Determination of Multiple φ-Torsion Angles in Proteins by Selective and Extensive 13C Labeling and Two-Dimensional Solid-State NMR

NASA Astrophysics Data System (ADS)

Hong, Mei

1999-08-01

We describe an approach to efficiently determine the backbone conformation of solid proteins that utilizes selective and extensive 13C labeling in conjunction with two-dimensional magic-angle-spinning NMR. The selective 13C labeling approach aims to reduce line broadening and other multispin complications encountered in solid-state NMR of uniformly labeled proteins while still enhancing the sensitivity of NMR spectra. It is achieved by using specifically labeled glucose or glycerol as the sole carbon source in the protein expression medium. For amino acids synthesized in the linear part of the biosynthetic pathways, [1-13C]glucose preferentially labels the ends of the side chains, while [2-13C]glycerol labels the Cα of these residues. Amino acids produced from the citric-acid cycle are labeled in a more complex manner. Information on the secondary structure of such a labeled protein was obtained by measuring multiple backbone torsion angles φ simultaneously, using an isotropic-anisotropic 2D correlation technique, the HNCH experiment. Initial experiments for resonance assignment of a selectively 13C labeled protein were performed using 15N-13C 2D correlation spectroscopy. From the time dependence of the 15N-13C dipolar coherence transfer, both intraresidue and interresidue connectivities can be observed, thus yielding partial sequential assignment. We demonstrate the selective 13C labeling and these 2D NMR experiments on a 8.5-kDa model protein, ubiquitin. This isotope-edited NMR approach is expected to facilitate the structure determination of proteins in the solid state.

Initial association of fresh microbial products to soil particles: a joint density fractionation and NanoSIMS study

NASA Astrophysics Data System (ADS)

Hatton, Pierre-Joseph; Remusat, Laurent; Brewer, Elizabeth; Derrien, Delphine

2014-05-01

While soil microorganisms are increasingly seen as shaping stable soil organic matter (OM) formation, the mechanisms controlling the attachment of microbial metabolites to soil particles are not fully understood yet. We investigate the spatial distribution of freshly produced microbial products among density-isolated fractions of soil using stable C and N isotopes and Nano-scale secondary ion mass spectrometry (NanoSIMS). A surface forest soil was amended with uniformly 13C/15N labeled glycine and incubated for 8 hours in gamma-irradiated and non-sterile soils. Sequential density fractionation was then performed to isolate various classes of aggregates and of single mineral particles. Eight hours after the labeled glycine addition, 7 % of the 13C and 15N was tightly bound to soil assemblages. Comparison of sterile and non-sterile treatments revealed that microbial activity was almost completely responsible for this rapid association (>85 %). The distributions of glycine-derived 13C and 15N, considered as markers of new microbial products, were mapped on particles of the non-sterile treatment using NanoSIMS. New microbial products were heterogeneously distributed and spatially decoupled at the surface of on soil particles. 13C microbial products were scarce and presumably within or in the vicinity of microbial cells. In contrast, 15N microbial products seemed evenly spread at the surface of soil particles, likely as soluble exoenzymes diffusing away from their parent cell. Macroscopic measurements among density fractions suggested that the diffusion of such 15N microbial products was spatially limited yet, because of pore space architecture. NanoSIMS images further allowed gaining insight into the attachment of the new microbial products on particle surfaces already covered by OM, in a multilayer fashion. Using an internal calibration method to determine C/N ratios of NanoSIMS images, we showed the preferential attachment of soluble microbial N-metabolites to N-rich mineral-attached OM (C/N ratios mostly < 16). Exceptions were found in dense particles, supposed to contained aluminium and iron (hydr)oxides, with the microbial N-metabolites apparently preferentially attached to C-rich mineral-attached OM (C/N ratios > 80). This work provided visual evidences that the attachment of new microbial products to the soil matrix is mediated by distinct processes for N-rich and C-rich metabolites. It also demonstrated that the pore space architecture has impact on the formation of stable OM by limiting the diffusion of soluble microbial metabolites and their access to reactive and stabilising surfaces.

13C-13C dipolar recoupling under very fast magic angle spinning in solid-state nuclear magnetic resonance: Applications to distance measurements, spectral assignments, and high-throughput secondary-structure determination

NASA Astrophysics Data System (ADS)

Ishii, Yoshitaka

2001-05-01

A technique is presented to recouple homonuclear dipolar couplings between dilute spin pairs such as 13C-13C systems under very fast magic angle spinning (MAS) in solid-state nuclear magnetic resonance (NMR) spectroscopy. The presented technique, finite pulse rf driven recoupling (fpRFDR), restores homonuclear dipolar interactions based on constructive usage of finite pulse-width effects in a phase- and symmetry-cycled π-pulse train in which a rotor-synchronous π pulse is applied every rotation period. The restored effective dipolar interaction has the form of a zero-quantum dipolar Hamiltonian for static solids, whose symmetry in spin space is different from that obtained by conventional rf driven recoupling (RFDR) techniques. It is demonstrated that the efficiency of recoupling by fpRFDR is not strongly dependent on chemical shift differences or resonance offsets in contrast to previous recoupling methods under very fast MAS. To realize distance measurements without effects of spin relaxation, a constant-time version of fpRFDR (CT-fpRFDR) is introduced, in which the effective evolution period is varied by refocusing dipolar evolution with a rotor-synchronized solid echo while the total recoupling period is kept constant. From CT-fpRFDR experiments at a spinning speed of 30.3 kHz in a field of 17.6 T, the 13C-13C distance of [1-13C]Ala-[1-13C]Gly-Gly was determined to be 3.27 Å, which agrees well with the value of 3.20 Å obtained by x-ray diffraction. Also, two-dimensional (2D) 13C/13C chemical-shift correlation NMR spectrum in a field of 9.4 T was obtained with fpRFDR for fibrils of the segmentally 13C- and 15N-labeled Alzheimer's β-Amyloid fragments, Aβ16-22 (residues 16-22 taken from the 40-residue Aβ peptide) in which Leu-17 through Ala-21 are uniformly 13C- and 15N-labeled. Most 13C resonances for the main chain as well as for the side chains are assigned based on 2D 13C/13C chemical-shift correlation patterns specific to amino-acid types. Examination of the obtained 13C chemical shifts revealed the formation of β-strand across the entire molecule of Aβ16-22. Possibility of high throughput determination of global main-chain structures based on 13C shifts obtained from 2D 13C/13C chemical-shift correlation under very fast MAS is also discussed for uniformly/segmentally 13C-labeled protein/peptide samples.

Production of isotopically labeled standards from a uniformly labeled precursor for quantitative volatile metabolomic studies.

PubMed

Gómez-Cortés, Pilar; Brenna, J Thomas; Sacks, Gavin L

2012-06-19

Optimal accuracy and precision in small-molecule profiling by mass spectrometry generally requires isotopically labeled standards chemically representative of all compounds of interest. However, preparation of mixed standards from commercially available pure compounds is often prohibitively expensive and time-consuming, and many labeled compounds are not available in pure form. We used a single-prototype uniformly labeled [U-(13)C]compound to generate [U-(13)C]-labeled volatile standards for use in subsequent experimental profiling studies. [U-(13)C]-α-Linolenic acid (18:3n-3, ALA) was thermally oxidized to produce labeled lipid degradation volatiles which were subsequently characterized qualitatively and quantitatively. Twenty-five [U-(13)C]-labeled volatiles were identified by headspace solid-phase microextraction-gas chromatography/time-of-flight mass spectrometry (HS-SPME-GC/TOF-MS) by comparison of spectra with unlabeled volatiles. Labeled volatiles were quantified by a reverse isotope dilution procedure. Using the [U-(13)C]-labeled standards, limits of detection comparable to or better than those of previous HS-SPME reports were achieved, 0.010-1.04 ng/g. The performance of the [U-(13)C]-labeled volatile standards was evaluated using a commodity soybean oil (CSO) oxidized at 60 °C from 0 to 15 d. Relative responses of n-decane, an unlabeled internal standard otherwise absent from the mixture, and [U-(13)C]-labeled oxidation products changed by up to 8-fold as the CSO matrix was oxidized, demonstrating that reliance on a single standard in volatile profiling studies yields inaccurate results due to changing matrix effects. The [U-(13)C]-labeled standard mixture was used to quantify 25 volatiles in oxidized CSO and low-ALA soybean oil with an average relative standard deviation of 8.5%. Extension of this approach to other labeled substrates, e.g., [U-(13)C]-labeled sugars and amino acids, for profiling studies should be feasible and can dramatically improve quantitative results compared to use of a single standard.

Exploiting Uniformly 13C-Labeled Carbohydrates for Probing Carbohydrate-Protein Interactions by NMR Spectroscopy.

PubMed

Nestor, Gustav; Anderson, Taigh; Oscarson, Stefan; Gronenborn, Angela M

2017-05-03

NMR of a uniformly 13 C-labeled carbohydrate was used to elucidate the atomic details of a sugar-protein complex. The structure of the 13 C-labeled Manα(1-2)Manα(1-2)ManαOMe trisaccharide ligand, when bound to cyanovirin-N (CV-N), was characterized and revealed that in the complex the glycosidic linkage torsion angles between the two reducing-end mannoses are different from the free trisaccharide. Distances within the carbohydrate were employed for conformational analysis, and NOE-based distance mapping between sugar and protein revealed that Manα(1-2)Manα(1-2)ManαOMe is bound more intimately with its two reducing-end mannoses into the domain A binding site of CV-N than with the nonreducing end unit. Taking advantage of the 13 C spectral dispersion of 13 C-labeled carbohydrates in isotope-filtered experiments is a versatile means for a simultaneous mapping of the binding interactions on both, the carbohydrate and the protein.

Maxwell AFB, Montgomery, Alabama. Revised Uniform Summary of Surface Weather Observations (RUSSWO)

DTIC Science & Technology

1974-09-19

VISION GAS . MAY 00-02 09 3,8 90 3,8 499 7,7 .1 11.6 3150 ___03.05, 1.1 4,0 1__ __ 4t, 15t6 139, *1 24#7 3188 0o.o13l ,5 397 __ 3t7 10,8 17,6 1__ 1 2497...WINDDIRECTION AND SPEED i (FROM HOURLY OBSERVATIONS) i ( ..1AXWELL AF B A-AA/HMM15C)MIRY 37m,72 sr-P STA TIONl STATIO lolUNK Tgllil "Ol N CLADA NOPAll (IS T

Application of unsymmetrical indirect covariance NMR methods to the computation of the (13)C <--> (15)N HSQC-IMPEACH and (13)C <--> (15)N HMBC-IMPEACH correlation spectra.

PubMed

Martin, Gary E; Hilton, Bruce D; Irish, Patrick A; Blinov, Kirill A; Williams, Antony J

2007-10-01

Utilization of long-range (1)H--(15)N heteronuclear chemical shift correlation has continually grown in importance since the first applications were reported in 1995. More recently, indirect covariance NMR methods have been introduced followed by the development of unsymmetrical indirect covariance processing methods. The latter technique has been shown to allow the calculation of hyphenated 2D NMR data matrices from more readily acquired nonhyphenated 2D NMR spectra. We recently reported the use of unsymmetrical indirect covariance processing to combine (1)H--(13)C GHSQC and (1)H--(15)N GHMBC long-range spectra to yield a (13)C--(15)N HSQC-HMBC chemical shift correlation spectrum that could not be acquired in a reasonable period of time without resorting to (15)N-labeled molecules. We now report the unsymmetrical indirect covariance processing of (1)H--(13)C GHMBC and (1)H--(15)N IMPEACH spectra to afford a (13)C--(15)N HMBC-IMPEACH spectrum that has the potential to span as many as six to eight bonds. Correlations for carbon resonances long-range coupled to a protonated carbon in the (1)H--(13)C HMBC spectrum are transferred via the long-range (1)H--(15)N coupling pathway in the (1)H--(15)N IMPEACH spectrum to afford a much broader range of correlation possibilities in the (13)C--(15)N HMBC-IMPEACH correlation spectrum. The indole alkaloid vincamine is used as a model compound to illustrate the application of the method. (c) 2007 John Wiley & Sons, Ltd.

Minot AFB, North Dakota. Revised Uniform Summary of Surface Weather Observations (RUSSWO). Parts A-F.

DTIC Science & Technology

1983-04-01

DEC I I. T! 8.61 57.9 6 1.5 21.1 1.3 19.8 37.9 71 TO~S8.3 2c.7t 2.1 26.8 .~5G* 18.A 1.? 8.% . 25. 8 43 USAFETAC 0 10 SIOL Al, P,.f usl 0-O .S n...N ih T m.p w.ato r. R[ .I. T0 F 32 F 6 F 73 IF 8 R P *93 F 1 ,To - Dry Bulb 4 W., SoIl 51 . -- - - -- - -- - - - - - ~ --- ----D..- - -~ GLOBAL

Serum carbon and nitrogen stable isotopes as potential biomarkers of dietary intake and their relation with incident type 2 diabetes: the EPIC-Norfolk study123

PubMed Central

Patel, Pinal S; Cooper, Andrew JM; O'Connell, Tamsin C; Kuhnle, Gunter GC; Kneale, Catherine K; Mulligan, Angela M; Luben, Robert N; Brage, Soren; Khaw, Kay-Tee; Wareham, Nicholas J; Forouhi, Nita G

2014-01-01

Background: Stable-isotope ratios of carbon (13C/12C, expressed as δ13C) and nitrogen (15N/14N, or δ15N) have been proposed as potential nutritional biomarkers to distinguish between meat, fish, and plant-based foods. Objective: The objective was to investigate dietary correlates of δ13C and δ15N and examine the association of these biomarkers with incident type 2 diabetes in a prospective study. Design: Serum δ13C and δ15N (‰) were measured by using isotope ratio mass spectrometry in a case-cohort study (n = 476 diabetes cases; n = 718 subcohort) nested within the European Prospective Investigation into Cancer and Nutrition (EPIC)–Norfolk population-based cohort. We examined dietary (food-frequency questionnaire) correlates of δ13C and δ15N in the subcohort. HRs and 95% CIs were estimated by using Prentice-weighted Cox regression. Results: Mean (±SD) δ13C and δ15N were −22.8 ± 0.4‰ and 10.2 ± 0.4‰, respectively, and δ13C (r = 0.22) and δ15N (r = 0.20) were positively correlated (P < 0.001) with fish protein intake. Animal protein was not correlated with δ13C but was significantly correlated with δ15N (dairy protein: r = 0.11; meat protein: r = 0.09; terrestrial animal protein: r = 0.12, P ≤ 0.013). δ13C was inversely associated with diabetes in adjusted analyses (HR per tertile: 0.74; 95% CI: 0.65, 0.83; P-trend < 0.001], whereas δ15N was positively associated (HR: 1.23; 95% CI: 1.09, 1.38; P-trend = 0.001). Conclusions: The isotope ratios δ13C and δ15N may both serve as potential biomarkers of fish protein intake, whereas only δ15N may reflect broader animal-source protein intake in a European population. The inverse association of δ13C but a positive association of δ15N with incident diabetes should be interpreted in the light of knowledge of dietary intake and may assist in identifying dietary components that are associated with health risks and benefits. PMID:24990425

1H, 15N and 13C NMR Assignments of Mouse Methionine Sulfoxide Reductase B2

PubMed Central

Breivik, Åshild S.; Aachmann, Finn L.; Sal, Lena S.; Kim, Hwa-Young; Del Conte, Rebecca; Gladyshev, Vadim N.; Dikiy, Alexander

2011-01-01

A recombinant mouse methionine-r-sulfoxide reductase 2 (MsrB2ΔS) isotopically labeled with 15N and 15N/13C was generated. We report here the 1H, 15N and 13C NMR assignments of the reduced form of this protein. PMID:19636904

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.

Spin-echo based diagonal peak suppression in solid-state MAS NMR homonuclear chemical shift correlation spectra

NASA Astrophysics Data System (ADS)

Wang, Kaiyu; Zhang, Zhiyong; Ding, Xiaoyan; Tian, Fang; Huang, Yuqing; Chen, Zhong; Fu, Riqiang

2018-02-01

The feasibility of using the spin-echo based diagonal peak suppression method in solid-state MAS NMR homonuclear chemical shift correlation experiments is demonstrated. A complete phase cycling is designed in such a way that in the indirect dimension only the spin diffused signals are evolved, while all signals not involved in polarization transfer are refocused for cancellation. A data processing procedure is further introduced to reconstruct this acquired spectrum into a conventional two-dimensional homonuclear chemical shift correlation spectrum. A uniformly 13C, 15N labeled Fmoc-valine sample and the transmembrane domain of a human protein, LR11 (sorLA), in native Escherichia coli membranes have been used to illustrate the capability of the proposed method in comparison with standard 13C-13C chemical shift correlation experiments.

Carbon and Nitrogen Input Fluxes in Subducting Sediments at the Izu-Bonin and Central America Convergent Margins

NASA Astrophysics Data System (ADS)

Li, L.; Sadofsky, S. J.; Bebout, G. E.

2003-12-01

We are investigating the N and C contents and isotope ratios in subducting sediment sections in the two MARGINS Subduction Factory focus sites, the Izu-Bonin (IB) and Central America (CA) convergent margins (using samples obtained on DSDP/ODP Legs 125, 170, 185, and 205). The sediments from IB (Site 1149, and Leg 129) contain 5 to 661 ppm N with δ 15NAir values of +2.5 to +8.2 per mil (weighted average +4.6 per mil). Reduced-C concentrations range from 0.02 to 0.35% with δ 13CPDB values from -28.1 to -21.7 per mil. Calcite in carbonate-rich layers has δ 13C of +1.7 to +2.8 per mil and δ 18OVSMOW of +28.5 to +29.7 per mil. In comparison with IB, the CA sediment section (Site 1039) has far higher N content (663 to 2380 ppm N with δ 15N of +3.9 to +7.1 per mil; weighted average +5.6 per mil). Calcite in Site 1039 carbonate-rich layers hasδ 13C of +0.1 to +3.0 per mil and δ 18O of +29.9 to +32.1 per mil. At Site 1149, down-section decrease in N content, accompanied by decrease in δ 15N and C/N, is thought to reflect diagenesis, whereas at Site 1039, down-section decrease in N content (near 2000 ppm at surface, near 1000 ppm at 150 km) occurs without an obvious shift in δ 15N (reduced C data not yet available). Based on the C-N concentration data we've obtained, sediment C-N input fluxes are estimated at, for the IB margin, 2.5x106 g/km.year for N, 1.7x107 g/km.year for reduced C, and 9.2x108 g/km.year for oxidized C. For the CA margin, we estimate input fluxes of 8.9x106 g/km.year for N, and 1.3x109 g/km.year for oxidized C (work on reduced C is underway). Our input fluxes for C and N differ significantly from previously published input fluxes for the two margins based on estimated subducting sediment C-N concentrations, but errors are large. For the CA margin, the sediment-only N input flux of 9.8x109 g/year (for the entire 1100 km trench length), based on our results for Site 1039, can be compared with the arc volcanic output flux of 8.1x109 g/year of Fischer et al. (2002, Science; N input flux of 6.4x109 g/year estimated by those authors), indicating the incomplete return of subducted N to the surface in arcs. The magnitude of the N input flux in altered oceanic crust remains unknown (work on AOC N-δ 15N is underway) but should also be considered in such comparisons. All estimates of this type assume uniformity in the incoming sediment section along-strike in active trenches (known not to be the case). Shifts from δ 15N values measured for the two sediment sections to values near +7 per mil for the deeply subducted sediment component as suggested by studies of volcanic gases (e.g., Fischer et al., 2002; Hilton et al., 2002) could be accomplished by moderate loss of isotopically light N during metamorphic devolatilization across forearcs.

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

USGS Publications Warehouse

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

2003-01-01

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

Starvation effects on nitrogen and carbon stable isotopes of animals: an insight from meta-analysis of fasting experiments

PubMed Central

Akamatsu, Fumikazu; González, Angélica L.

2017-01-01

Nitrogen and carbon stable isotopic compositions (δ15N and δ13C) of consumers have been used for physiological and food web studies. Previous studies have shown δ15N and δ13C values are affected by several biological and environmental factors during starvation, but the generality of the effect of starvation on δ15N and δ13C values has not yet been tested. Here, we performed a meta-analysis to evaluate the effects of starvation on δ15N and δ13C values of consumers, and the underlying factors that may explain the observed variation. The δ15N and δ13C values were calculated as the differences between the final δ15N and δ13C values of consumers (post-starvation) and the pre-starvation values on each experiment. Our meta-analysis showed a large variation in the δ15N and δ13C values of consumers (δ15N range: –0.82 to 4.30‰; mean: 0.47‰ and δ13C range: –1.92 to 2.62‰; mean: 0.01‰). The δ15N values of most consumers increased along the length of the starvation period and were influenced by nitrogen excretion and thermoregulation types, probably because differences in nitrogen metabolism and thermoregulation affect nitrogen processing and excretion rates. None of our predictor variables accounted for the variation in δ13C values, which showed both increases and decreases due to fasting. Our findings suggest that starvation results in changes in consumer δ15N values which are mainly explained by the length of the fasting period and by nitrogen and energy metabolism, but the underlying mechanisms of the starvation effects on δ13C values seem to be more complex than previously thought. PMID:28879005

Structure of the Putative 32 kDa Myrosinase Binding Protein from Arabidopsis (At3g16450.1) Determined by SAIL-NMR

PubMed Central

Takeda, Mitsuhiro; Sugimori, Nozomi; Torizawa, Takuya; Terauchi, Tsutomu; Ono, Akira Mei; Yagi, Hirokazu; Yamaguchi, Yoshiki; Kato, Koichi; Ikeya, Teppei; Jee, JunGoo; Güntert, Peter; Aceti, David J.; Markley, John L.; Kainosho, Masatsune

2009-01-01

The product of gene At3g16450.1 from Arabidopsis thaliana is a 32 kDa, 299-residue protein classified as resembling a myrosinase-binding protein (MyroBP). MyroBPs are found in plants as part of a complex with the glucosinolate-degrading enzyme, myrosinase, and are suspected to play a role in myrosinase-dependent defense against pathogens. Many MyroBPs and MyroBP-related proteins are composed of repeated homologous sequences with unknown structure. We report here the three-dimensional structure of the At3g16450.1 protein from Arabidopsis, which consists of two tandem repeats. Because the size of the protein is larger than that amenable to high-throughput analysis by uniformly 13C/15N labeling methods, we used our stereo-array isotope labeling (SAIL) technology to prepare an optimally 2H/13C/15N-labeled sample. NMR data sets collected with the SAIL-protein enabled us to assign 1H, 13C and 15N chemical shifts to 95.5% of all atoms, even at the low concentration (0.2 mM) of the protein product. We collected additional NOESY data and solved the three-dimensional structure with the CYANA software package. The structure, the first for a MyroBP family member, revealed that the At3g16450.1 protein consists of two independent, but similar, lectin-fold domains composed of three β-sheets. PMID:19021763

Structure of the putative 32 kDa myrosinase-binding protein from Arabidopsis (At3g16450.1) determined by SAIL-NMR.

PubMed

Takeda, Mitsuhiro; Sugimori, Nozomi; Torizawa, Takuya; Terauchi, Tsutomu; Ono, Akira M; Yagi, Hirokazu; Yamaguchi, Yoshiki; Kato, Koichi; Ikeya, Teppei; Jee, Jungoo; Güntert, Peter; Aceti, David J; Markley, John L; Kainosho, Masatsune

2008-12-01

The product of gene At3g16450.1 from Arabidopsis thaliana is a 32 kDa, 299-residue protein classified as resembling a myrosinase-binding protein (MyroBP). MyroBPs are found in plants as part of a complex with the glucosinolate-degrading enzyme myrosinase, and are suspected to play a role in myrosinase-dependent defense against pathogens. Many MyroBPs and MyroBP-related proteins are composed of repeated homologous sequences with unknown structure. We report here the three-dimensional structure of the At3g16450.1 protein from Arabidopsis, which consists of two tandem repeats. Because the size of the protein is larger than that amenable to high-throughput analysis by uniform (13)C/(15)N labeling methods, we used stereo-array isotope labeling (SAIL) technology to prepare an optimally (2)H/(13)C/(15)N-labeled sample. NMR data sets collected using the SAIL protein enabled us to assign (1)H, (13)C and (15)N chemical shifts to 95.5% of all atoms, even at a low concentration (0.2 mm) of protein product. We collected additional NOESY data and determined the three-dimensional structure using the cyana software package. The structure, the first for a MyroBP family member, revealed that the At3g16450.1 protein consists of two independent but similar lectin-fold domains, each composed of three beta-sheets.

Nutritional assessment using stable isotope ratios of carbon and nitrogen in the scalp hair of geriatric patients who received enteral and parenteral nutrition formulas.

PubMed

Hayasaka, M; Ogasawara, H; Hotta, Y; Tsukagoshi, K; Kimura, O; Kura, T; Tarumi, T; Muramatsu, H; Endo, T

2017-12-01

The δ 13 C and δ 15 N values in the scalp hair of geriatric patients in Japan who received the enteral or parenteral nutrition formula were measured to assess nutritional status. The relations among δ 13 C, δ 15 N, calorie intake, BMI, albumin concentration, total cholesterol (T-CHO) and geriatric nutritional risk index (GNRI) in the patients were investigated. Furthermore, the enrichment of δ 13 C and δ 15 N from the nutrients to the hair was investigated. The δ 13 C values in the hair of patients who received enteral nutrition decreased with decreases in the calories received, while the δ 15 N values increased, suggesting malnutrition in some patients with a low calorie intake due to a negative nitrogen balance. The distribution of patients with a low calorie intake (below 20 kcal/kg/day) when δ 13 C was plotted against δ 15 N differed from that of control subjects, but the distribution of patients with a high calorie intake (above 20 kcal/kg/day) was similar to that of control subjects. No significant differences were observed in BMI, albumin concentration, T-CHO or GNRI between the low and high calorie groups. The enrichment of δ 13 C and δ 15 N from the enteral nutrients to the hair were inversely correlated with the δ 13 C and δ 15 N in the enteral nutrients. The enrichment levels of δ 13 C and δ 15 N tended to be higher and lower, respectively, in the high calorie group. On the other hand, the δ 13 C and δ 15 N values in the hair of patients who received parenteral nutrition were higher and lower than those in the control subjects and in the patients who received enteral nutrition, respectively, reflecting the higher δ 13 C and lower δ 15 N contents of the parenteral nutrients. The δ 13 C and δ 15 N values in the hair of patients who received enteral nutrition may be effective indicators for evaluating the long-term nutritional status of geriatric patients. A calorie intake of 20 kcal/kg/day may be a cut-off value for malnutrition in Japanese geriatric patients receiving enteral nutrition. However, caution is necessary when dealing with patients switching from parental nutrition as parenteral nutrition resulted in different changes in δ 13 C and δ 15 N. The enrichment levels of δ 13 C and δ 15 N from the enteral nutrients to the hair may be inversely correlated with the δ 13 C and δ 15 N values of enteral nutrients and vary according to the calorie intake. Copyright © 2016 Elsevier Ltd and European Society for Clinical Nutrition and Metabolism. All rights reserved.

High Resolution 13C MRI With Hyperpolarized Urea: In Vivo T2 Mapping and 15N Labeling Effects

PubMed Central

Reed, Galen D.; von Morze, Cornelius; Bok, Robert; Koelsch, Bertram L.; Van Criekinge, Mark; Smith, Kenneth J.; Shang, Hong; Larson, Peder E. Z.; Kurhanewicz, John; Vigneron, Daniel B.

2014-01-01

13C steady state free precession (SSFP) magnetic resonance imaging and effective spin-spin relaxation time (T2) mapping were performed using hyperpolarized [13C] urea and [13C, 15N2] urea injected intravenously in rats. 15N labeling gave large T2 increases both in solution and in vivo due to the elimination of a strong scalar relaxation pathway. The T2 increase was pronounced in the kidney, with [13C, 15N2] urea giving T2 values of 6.3±1.3 s in the cortex and medulla, and 11±2 s in the renal pelvis. The measured T2 in the aorta was 1.3±0.3 s. [13C] urea showed shortened T2 values in the kidney of 0.23±0.03 s compared to 0.28±0.03 s measured in the aorta. The enhanced T2 of [13C, 15N2] urea was utilized to generate large signal enhancement by SSFP acquisitions with flip angles approaching the fully refocused regime. Projection images at 0.94 mm in-plane resolution were acquired with both urea isotopes, with [13C, 15N2] urea giving a greater than four-fold increase in signal-to-noise ratio [13C] over urea. PMID:24235273

Enhancing the understanding of earthworm feeding behaviour via the use of fatty acid delta13C values determined by gas chromatography-combustion-isotope ratio mass spectrometry.

PubMed

Dungait, Jennifer A J; Briones, Maria J I; Bol, Roland; Evershed, Richard P

2008-06-01

Litter-dwelling (epigeic) Lumbricus rubellus and soil-dwelling (endogeic) Allolobophora chlorotica earthworms were observed aggregating under C(3) (delta(13)C = -31.3 per thousand; delta(15)N = 10.7 per thousand) and C(4) (delta(13)C = -12.6 per thousand; delta(15)N = 7.5 per thousand) synthetic dung pats applied to a temperate grassland (delta(13)C = -30.3 per thousand; delta(15)N = 5.7 per thousand) in an experiment carried out for 372 days. Bulk delta(13)C values of earthworms collected from beneath either C(3) or C(4) dung after 28, 56, 112 and 372 days demonstrated that (i) L. rubellus beneath C(4) dung were significantly (13)C-enriched after 56 days (delta(13)C = -23.8 per thousand) and 112 days (delta(13)C = -22.4 per thousand) compared with those from C(3) dung treatments (56 days, delta(13)C = -26.5 per thousand; 112 days, delta(13)C = -27.0 per thousand), and (ii) A. chlorotica were 2.1 per thousand (13)C-enriched (delta(13)C = -24.2 per thousand) relative to those from C(3) dung (delta(13)C = -26.3 per thousand) treatments after 372 days. Bulk delta(15)N values did not suggest significant uptake of dung N by either species beneath C(3) or C(4) dung, but showed that the endogeic species (total mean delta(15)N = 3.3 per thousand) had higher delta(15)N values than the epigeic species (total mean delta(15)N = 5.4 per thousand). Although the two species exhibited similar fatty acid profiles, individual fatty acid delta(13)C values revealed extensive routing of dietary C into body tissue of L. rubellus, but minor incorporation into A. chlorotica. In particular, the direct incorporation of microbial biomarker fatty acids (iC(17:0), aC(17:0)) from (13)C-labelled dung in situ, the routing of dung C into de novo synthesised compounds (iC(20:4)(omega)(6),C(20:5)(omega)(3), and the assimilation of essential fatty acids ((C(18:1)(omega)(9), C(18:1)(omega(7), C(18:2)(omega(6), C(18:3)(omega)(3)) derived from dung, were determined. John Wiley & Sons, Ltd

STELLAR ORIGINS OF EXTREMELY {sup 13}C- AND {sup 15}N-ENRICHED PRESOLAR SIC GRAINS: NOVAE OR SUPERNOVAE?

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

Liu, Nan; Nittler, Larry R.; Alexander, Conel M. O’D.

Extreme excesses of {sup 13}C ({sup 12}C/{sup 13}C < 10) and {sup 15}N ({sup 14}N/{sup 15}N < 20) in rare presolar SiC grains have been considered diagnostic of an origin in classical novae, though an origin in core collapse supernovae (CCSNe) has also been proposed. We report C, N, and Si isotope data for 14 submicron- to micron-sized {sup 13}C- and {sup 15}N-enriched presolar SiC grains ({sup 12}C/{sup 13}C < 16 and {sup 14}N/{sup 15}N < ∼100) from Murchison, and their correlated Mg–Al, S, and Ca–Ti isotope data when available. These grains are enriched in {sup 13}C and {sup 15}N,more » but with quite diverse Si isotopic signatures. Four grains with {sup 29,30}Si excesses similar to those of type C SiC grains likely came from CCSNe, which experienced explosive H burning occurred during explosions. The independent coexistence of proton- and neutron-capture isotopic signatures in these grains strongly supports heterogeneous H ingestion into the He shell in pre-supernovae. Two of the seven putative nova grains with {sup 30}Si excesses and {sup 29}Si depletions show lower-than-solar {sup 34}S/{sup 32}S ratios that cannot be explained by classical nova nucleosynthetic models. We discuss these signatures within the CCSN scenario. For the remaining five putative nova grains, both nova and supernova origins are viable because explosive H burning in the two stellar sites could result in quite similar proton-capture isotopic signatures. Three of the grains are sub-type AB grains that are also {sup 13}C enriched, but have a range of higher {sup 14}N/{sup 15}N. We found that {sup 15}N-enriched AB grains (∼50 < {sup 14}N/{sup 15}N < ∼100) have distinctive isotopic signatures compared to putative nova grains, such as higher {sup 14}N/{sup 15}N, lower {sup 26}Al/{sup 27}Al, and lack of {sup 30}Si excess, indicating weaker proton-capture nucleosynthetic environments.« less

Effect of body size and body mass on δ 13 C and δ 15 N in coastal fishes and cephalopods

NASA Astrophysics Data System (ADS)

Vinagre, C.; Máguas, C.; Cabral, H. N.; Costa, M. J.

2011-11-01

Carbon and nitrogen isotopes have been widely used in the investigation of trophic relations, energy pathways, trophic levels and migrations, under the assumption that δ 13C is independent of body size and that variation in δ 15N occurs exclusively due to ontogenetic changes in diet and not body size increase per se. However, several studies have shown that these assumptions are uncertain. Data from food-webs containing an important number of species lack theoretical support on these assumptions because very few species have been tested for δ 13C and δ 15N variation in captivity. However, if sampling comprises a wide range of body sizes from various species, the variation of δ 13C and δ 15N with body size can be investigated. While correlation between body size and δ 13C and δ 15N can be due to ontogenetic diet shifts, stability in such values throughout the size spectrum can be considered an indication that δ 13C and δ 15N in muscle tissues of such species is independent of body size within that size range, and thus the basic assumptions can be applied in the interpretation of such food webs. The present study investigated the variation in muscle δ 13C and δ 15N with body size and body mass of coastal fishes and cephalopods. It was concluded that muscle δ 13C and δ 15N did not vary with body size or mass for all bony fishes with only one exception, the dragonet Callionymus lyra. Muscle δ 13C and δ 15N also did not vary with body size or mass in cartilaginous fishes and cephalopods, meaning that body size/mass per se have no effect on δ 13C or δ 15N, for most species analysed and within the size ranges sampled. The assumption that δ 13C is independent of body size and that variation in δ 15N is not affected by body size increase per se was upheld for most organisms and can be applied to the coastal food web studied taking into account that C. lyra is an exception.

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

NASA Astrophysics Data System (ADS)

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

1987-06-01

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

Investigations into the \\delta 15N and \\delta 13C of POM, Primary Producers, and Filter Feeders in the Florida Keys Coral Reef Tract

NASA Astrophysics Data System (ADS)

Lamb, K. A.; Swart, P. K.

2004-12-01

In order to examine the possible influences of anthropogenic wastes on the Florida Keys coral reef tract, water column particulate organic matter \\(POM\\), primary producers, and filter feeders were sampled from within the coastal waters of the reef tract, and analyzed for \\delta 15N and \\delta 13C isotopic composition. The POM was found to have a mean \\delta 15N value of +4.13\\permil (\\pm 1.03\\permil\\) and a mean \\delta 13C value of -19.93\\permil (\\pm 0.58\\permil). The \\delta 13C values for POM across the entire reef tract were heavier inshore \\(avg \\delta 13C = -18.29\\permil \\(\\pm 1.04\\permil\\)\\) and became lighter offshore \\(avg \\delta 13C = -21.41\\permil \\(\\pm 0.89\\permil\\)\\), which is consistent with influences from benthic algae/seagrass closer to shore in contrast to open-marine influences offshore. The \\delta 15N values for POM were neither temporally nor spatially interrelated, as the data showed no clear trend moving in either the inshore or offshore direction. Instead, our \\delta 15N values for POM reflect a combined influence from nitrogen fixation \\(\\approx0\\permil\\), zooplankton and other suspended particles, and not anthropogenic wastes \\(>+10\\permil\\), as other authors claim. The mean isotopic composition of various primary producers suggests a nitrogen fixation source of nutrients to the reef system (Halimeda sp. (\\delta 15N = 2.43\\permil; \\delta 13C = -18.04\\permill), Dictyota sp. (\\delta 15N = +2.86\\permil; \\delta 13C = -16.30\\permil), Thalassia sp. (\\delta 15N = 2.39\\permil; \\delta 13C = -10.32\\permil)), while filter feeders were found to have a mean isotopic composition more similar to POM values (sponge \\delta 15N = 4.95\\permil; \\delta 13C = -18.02\\permil). Our data simply do not appear to show evidence of anthropogenic influence on the Florida Keys reef tract. Further more, we suggest that \\delta 15N values of +4\\permil, which have recently been suggested to indicate anthropogenic influences are not, in fact, indicative of sewage.

Variability in the fractionation of stable isotopes during degradation of two intertidal red algae

NASA Astrophysics Data System (ADS)

Hill, Jaclyn M.; McQuaid, Christopher D.

2009-04-01

Macroalgae contribute to intertidal food webs primarily as detritus, with unclear implications for food web studies using stable isotope analysis. We examined differences in the thallus parts of two South African rhodophytes ( Gelidium pristoides and Hypnea spicifera) and changes in overall δ13C, δ15N signatures and C:N ratios during degradation in both the field and laboratory. We hypothesized that both degrading macroalgal tissue and macroalgal-derived suspended particulate material (SPM) would show negligible changes in δ13C, but enriched δ15N signatures and lower C:N ratios relative to healthy plants. Only C:N laboratory ratios conformed to predictions, with both species of macroalgae showing decomposition related changes in δ13C and significant depletions in δ15N in both the field and laboratory. In the laboratory, algal tissue and SPM from each species behaved similarly (though some effects were non-significant) but with differing strengths. Gelidium pristoides δ13C increased and C:N ratios decreased over time in tissue and SPM; δ15N became depleted only in SPM. Hypnea spicifera, δ13C, δ15N and C:N ratios all decreased during degradation in both SPM and algae. Over 60 days in the field, δ13C was depleted in both species (1-2‰) and in naturally senescent Gelidium pristoides fronds. δ15N was depleted in Hypnea spicifera (approx. 1‰), while C:N ratios of both species were unaffected. The two species differed in δ13C, δ15N and C:N after degradation, but only in C:N beforehand. We suggest isotope changes in the laboratory mainly reflect microbial effects, while in the field these are combined with leaching due to constant water replenishment and agitation. Differences between these two species in the isotope responses to degradation highlight the difficulty of linking the signature of SPM to its multiple sources.

Adsorption and wetting characterization of hydrophobic SBA-15 silicas.

PubMed

Bernardoni, Frank; Fadeev, Alexander Y

2011-04-15

This work describes adsorption and wetting characterization of hydrophobic ordered mesoporous silicas (OMSs) with the SBA-15 motif. Three synthetic approaches to prepare hydrophobic SBA-15 silicas were explored: grafting with (1) covalently-attached monolayers (CAMs) of C(n)H(2)(n+1)Si(CH(3))(2)N(CH(3))(2), (2) self-assembled monolayers (SAMs) of C(n)H(2)(n+1)Si(OEt)(3), and (3) direct ("one-pot") co-condensation of TEOS with C(n)H(2)(n+1)Si(OEt)(3) in presence of P123 (n=1-18). The materials prepared were characterized by nitrogen adsorption, TEM, and chemical analysis. The surface properties of the materials were assessed by water contact angles (CAs) and by BET C constants. The results showed that, while loadings of the alkyl groups (%C) were comparable, the surface properties and pore ordering of the materials prepared through different methods were quite different. The best quality hydrophobic surfaces were prepared for SBA-15 grafted with CAMs of alkylsilanes. For these materials, the water CAs were above ∼120°/100° (adv/rec) and BET C constants were in the range of ∼15-25, indicating uniform low-energy surfaces of closely packed alkyl groups on external and internal surfaces of the pores respectively. Moreover, surfaces grafted with the long-chained (C(12)-C(18)) silanes showed super-hydrophobic behavior (CAs∼150-180°) and extremely low adhesion for water. The pore uniformity of parental SBA-15 was largely preserved and the pore volume and pore diameter were consistent with the formation of a single layer of alkylsilyl groups inside the pores. Post-synthesis grafting of SBA-15 with SAMs worked not as well as CAMs: the surfaces prepared demonstrated lower water CAs and higher BET C constants, thereby indicating a small amount of accessible polar groups (Si-OH) related to packing constrains for SAMs supported on highly curved surfaces of mesopores. The co-condensation method produced substantially more disordered materials and less hydrophobic surfaces than any of the grafting methods. The surfaces of these materials showed low water CAs and high BET C constants (∼100-200) thereby demonstrating a non-uniform surface coverage and presence of unmodified silica. It is concluded that CAMs chemistry is the most efficient approach in preparation of the functionalized OMS materials with uniform surfaces and pores. Copyright © 2011 Elsevier Inc. All rights reserved.

Backbone resonance assignments of the PRYSPRY domain of TRIM25.

PubMed

Kong, Chen; Penumutchu, Srinivasa R; Hung, Kuo-Wei; Huang, Huiying; Lin, Tianwei; Yu, Chin

2015-10-01

TRIM25 is a member of the tripartite motif (TRIM) family and has been implicated in the regulation of innate immune signaling via the RIG-I (retinoic acid-inducible gene-I) pathway for antiviral defense. As the essential first step towards the structural and functional characterization of the TRIM25/RIG-I interaction, the backbone resonance of the PRYSPRY domain of TRIM25 is assigned here based on triple-resonance experiments using uniformly [(2)H, (13)C, (15)N]-labeled protein.

A robust heteronuclear dipolar recoupling method comparable to TEDOR for proteins in magic-angle spinning solid-state NMR

NASA Astrophysics Data System (ADS)

Zhang, Zhengfeng; Li, Jianping; Chen, Yanke; Xie, Huayong; Yang, Jun

2017-12-01

In this letter, we propose a robust heteronuclear dipolar recoupling method for proteins in magic-angle spinning (MAS) solid-state NMR. This method is as simple, robust and efficient as the well-known TEDOR in the aspect of magnetization transfer between 15N and 13C. Deriving from our recent band-selective dual back-to-back pulses (DBP) (Zhang et al., 2016), this method uses new phase-cycling schemes to realize broadband DBP (Bro-DBP). For broadband 15N-13C magnetization transfer (simultaneous 15N → 13C‧ and 15N → 13Cα), Bro-DBP has almost the same 15N → 13Cα efficiency while offers 30-40% enhancement on 15N → 13C‧ transfer, compared to TEDOR. Besides, Bro-DBP can also be used as a carbonyl (13C‧)-selected method, whose 15N → 13C‧ efficiency is up to 1.7 times that of TEDOR and is also higher than that of band-selective DBP. The performance of Bro-DBP is demonstrated on the N-formyl-[U-13C,15N]-Met-Leu-Phe-OH (fMLF) peptide and the U-13C, 15N labeled β1 immunoglobulin binding domain of protein G (GB1) microcrystalline protein. Since Bro-DBP is as robust, simple and efficient as TEDOR, we believe it is very useful for protein studies in MAS solid-state NMR.

Mutual orientation of three magnetic tensors in a polycrystalline dipeptide by dipole-modulated 15N chemical shift spectroscopy

NASA Astrophysics Data System (ADS)

Hartzell, C. J.; Pratum, T. K.; Drobny, G.

1987-10-01

This study demonstrates the mutual orientation of three tensor interactions in a single NMR experiment. The orientation of the 15N chemical shift tensor relative to the molecular frame has thus been determined in polycrystalline L-[1-13C] alanyl-L-[15N] alanine. The 13C-15N and 15N-1H dipole interactions are determined using the 1H dipole-modulated, 13C dipole-coupled 15N spectrum obtained as a transform of the data in t2. From simulations of the experimental spectra, two sets of polar angles have been determined relating the 13C-15N and 15N-1H dipoles to the 15N chemical shift tensor. The values determined are βCN =106°, αCN =5° and βNH =-19°, αNH =12°. The experiment verifies, without reference to single crystal data, that σ33 lies in the peptide plane and σ22 is nearly perpendicular to the plane.

Biosynthesis of highly enriched 13C-lycopene for human metabolic studies using repeated batch tomato cell culturing with 13C-glucose

PubMed Central

Moran, Nancy E.; Rogers, Randy B.; Lu, Chi-Hua; Conlon, Lauren E.; Lila, Mary Ann; Clinton, Steven K.; Erdman, John W.

2013-01-01

While putative disease-preventing lycopene metabolites are found in both tomato (Solanum lycopersicum) products and in their consumers, mammalian lycopene metabolism is poorly understood. Advances in tomato cell culturing techniques offer an economical tool for generation of highly-enriched 13C-lycopene for human bioavailability and metabolism studies. To enhance the 13C-enrichment and yields of labeled lycopene from the hp-1 tomato cell line, cultures were first grown in 13C-glucose media for three serial batches and produced increasing proportions of uniformly labeled lycopene (14.3 +/− 1.2 %, 39.6 +/− 0.5 %, and 48.9 +/− 1.5% with consistent yields (from 5.8 to 9 mg/L). An optimized 9-day-long 13C-loading and 18-day-long labeling strategy developed based on glucose utilization and lycopene yields, yielded 13C-lycopene with 93% 13C isotopic purity, and 55% of isotopomers were uniformly labeled. Furthermore, an optimized acetone and hexane extraction led to a four-fold increase in lycopene recovery from cultures compared to a standard extraction. PMID:23561155

Human SLC26A4/Pendrin STAS domain is a nucleotide-binding protein: Refolding and characterization for structural studies.

PubMed

Sharma, Alok K; Krieger, Tobias; Rigby, Alan C; Zelikovic, Israel; Alper, Seth L

2016-12-01

Mutations in the human SLC26A4/Pendrin polypeptide (hPDS) cause Pendred Syndrome /DFNB4, syndromic deafness with enlargement of the vestibular aqueduct and low-penetrance goiter. Here we present data on cloning, protein overexpression and purification, refolding, and biophysical characterization of the recombinant hPDS STAS domain lacking its intrinsic variable sequence (STAS-ΔIVS). We report a reproducible protein refolding protocol enabling milligram scale expression and purification of uniformly 15 N- and 13 C /15 N-enriched hPDS STAS-ΔIVS domain suitable for structural characterization by solution NMR. Circular dichroism, one-dimensional 1 H, two-dimensional 1 H- 15 N HSQC, and 1 H- 13 C HSQC NMR spectra confirmed the well-folded state of purified hPDS STAS-ΔIVS in solution. Heteronuclear NMR chemical shift perturbation of select STAS-ΔIVS residues by GDP was observed at fast-to-intermediate NMR time scales. Intrinsic tryptophan fluorescence quench experiments demonstrated GDP binding to hPDS STAS-ΔIVS with K d of 178 μM. These results are useful for structure/function characterization of hPDS STAS, the cytoplasmic subdomain of the congenital deafness protein, pendrin, as well as for studies of other mammalian STAS domains.

Amino Acid Selective 13C Labeling and 13C Scrambling Profile Analysis of Protein α and Side-Chain Carbons in Escherichia coli Utilized for Protein Nuclear Magnetic Resonance.

PubMed

Sugiki, Toshihiko; Furuita, Kyoko; Fujiwara, Toshimichi; Kojima, Chojiro

2018-06-20

Amino acid selective isotope labeling is an important nuclear magnetic resonance technique, especially for larger proteins, providing strong bases for the unambiguous resonance assignments and information concerning the structure, dynamics, and intermolecular interactions. Amino acid selective 15 N labeling suffers from isotope dilution caused by metabolic interconversion of the amino acids, resulting in isotope scrambling within the target protein. Carbonyl 13 C atoms experience less isotope scrambling than the main-chain 15 N atoms do. However, little is known about the side-chain 13 C atoms. Here, the 13 C scrambling profiles of the Cα and side-chain carbons were investigated for 15 N scrambling-prone amino acids, such as Leu, Ile, Tyr, Phe, Thr, Val, and Ala. The level of isotope scrambling was substantially lower in 13 Cα and 13 C side-chain labeling than in 15 N labeling. We utilized this reduced scrambling-prone character of 13 C as a simple and efficient method for amino acid selective 13 C labeling using an Escherichia coli cold-shock expression system and high-cell density fermentation. Using this method, the 13 C labeling efficiency was >80% for Leu and Ile, ∼60% for Tyr and Phe, ∼50% for Thr, ∼40% for Val, and 30-40% for Ala. 1 H- 15 N heteronuclear single-quantum coherence signals of the 15 N scrambling-prone amino acid were also easily filtered using 15 N-{ 13 Cα} spin-echo difference experiments. Our method could be applied to the assignment of the 55 kDa protein.

Alma Observations of HCN and its Isotopologues on Titan

NASA Technical Reports Server (NTRS)

Molter, Edward M.; Nixon, C. A.; Cordiner, M. A.; Serigano, J.; Irwin, P. G. J.; Teanby, N. A.; Charnley, S. B.; Lindberg, J. E.

2016-01-01

We present sub-millimeter spectra of HCN isotopologues on Titan, derived from publicly available ALMA flux calibration observations of Titan taken in early 2014. We report the detection of a new HCN isotopologue on Titan, H13C15N, and confirm an earlier report of detection of DCN. We model high signal-to-noise observations of HCN, H13CN, HC15N, DCN, and H13C15N to derive abundances and infer the following isotopic ratios: 12C/13C = 89.8 +/- 2.8, 14N/15N = 72.3 +/- 2.2, D/H = (2.5 +/- 0.2) × 10-4, and HCN/H13C15N = 5800 +/- 270 (1sigma errors). The carbon and nitrogen ratios are consistent with and improve on the precision of previous results, confirming a factor of approximately 2.3 elevation in 14N/15N in HCN compared to N2 and a lack of fractionation in 12C/13C from the protosolar value. This is the first published measurement of D/H in a nitrile species on Titan, and we find evidence for a factor of approximately 2 deuterium enrichment in hydrogen cyanide compared to methane. The isotopic ratios we derive may be used as constraints for future models to better understand the fractionation processes occurring in Titan's atmosphere.

Long-term carbon and nitrogen dynamics at SPRUCE revealed through stable isotopes in peat profiles

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

Hobbie, Erik A.; Chen, Janet; Hanson, Paul J.

Peatlands encode information about past vegetation dynamics, climate, and microbial processes. Here, we used δ 15N and δ 13C patterns from 16 peat profiles to deduce how the biogeochemistry of the Marcell S1 forested bog in northern Minnesota responded to environmental and vegetation change over the past ~10 000 years. In multiple regression analyses, δ 15N and δ 13C correlated strongly with depth, plot location, C/N, %N, and each other. Correlations with %N, %C, C/N, and the other isotope accounted for 80 % of variance for δ 15N and 38 % of variance for δ 13C, reflecting N and C losses.more » In contrast, correlations with depth and topography (hummock or hollow) reflected peatland successional history and climate. Higher δ 15N in plots closer to uplands may reflect upland-derived DON inputs and accompanying shifts in N dynamics in the lagg drainage area surrounding the bog. The Suess effect (declining δ 13CO 2 since the Industrial Revolution) lowered δ 13C in recent surficial samples. High δ 15N from –35 to –5 cm probably indicated the depth of ectomycorrhizal activity after tree colonization of the peatland over the last 400 years, as confirmed by the occasional presence of wood down to –35 cm depth. High δ 13C at ~4000 years BP (–65 to –105 cm) could reflect a transition at that time to slower rates of peat accumulation, when 13C discrimination during peat decomposition may increase in importance. Low δ 13C and high δ 15N at –213 and –225 cm (~8500 years BP) corresponded to a warm period during a sedge-dominated rich fen stage. As a result, the above processes appear to be the primary drivers of the observed isotopic patterns, whereas there was no clear evidence for methane dynamics influencing δ 13C patterns.« less

Long-term carbon and nitrogen dynamics at SPRUCE revealed through stable isotopes in peat profiles

NASA Astrophysics Data System (ADS)

Hobbie, Erik A.; Chen, Janet; Hanson, Paul J.; Iversen, Colleen M.; McFarlane, Karis J.; Thorp, Nathan R.; Hofmockel, Kirsten S.

2017-05-01

Peatlands encode information about past vegetation dynamics, climate, and microbial processes. Here, we used δ15N and δ13C patterns from 16 peat profiles to deduce how the biogeochemistry of the Marcell S1 forested bog in northern Minnesota responded to environmental and vegetation change over the past ˜ 10 000 years. In multiple regression analyses, δ15N and δ13C correlated strongly with depth, plot location, C / N, %N, and each other. Correlations with %N, %C, C / N, and the other isotope accounted for 80 % of variance for δ15N and 38 % of variance for δ13C, reflecting N and C losses. In contrast, correlations with depth and topography (hummock or hollow) reflected peatland successional history and climate. Higher δ15N in plots closer to uplands may reflect upland-derived DON inputs and accompanying shifts in N dynamics in the lagg drainage area surrounding the bog. The Suess effect (declining δ13CO2 since the Industrial Revolution) lowered δ13C in recent surficial samples. High δ15N from -35 to -55 cm probably indicated the depth of ectomycorrhizal activity after tree colonization of the peatland over the last 400 years, as confirmed by the occasional presence of wood down to -35 cm depth. High δ13C at ˜ 4000 years BP (-65 to -105 cm) could reflect a transition at that time to slower rates of peat accumulation, when 13C discrimination during peat decomposition may increase in importance. Low δ13C and high δ15N at -213 and -225 cm ( ˜ 8500 years BP) corresponded to a warm period during a sedge-dominated rich fen stage. The above processes appear to be the primary drivers of the observed isotopic patterns, whereas there was no clear evidence for methane dynamics influencing δ13C patterns.

Long-term carbon and nitrogen dynamics at SPRUCE revealed through stable isotopes in peat profiles

DOE PAGES

Hobbie, Erik A.; Chen, Janet; Hanson, Paul J.; ...

2017-05-17

Peatlands encode information about past vegetation dynamics, climate, and microbial processes. Here, we used δ 15N and δ 13C patterns from 16 peat profiles to deduce how the biogeochemistry of the Marcell S1 forested bog in northern Minnesota responded to environmental and vegetation change over the past ~10 000 years. In multiple regression analyses, δ 15N and δ 13C correlated strongly with depth, plot location, C/N, %N, and each other. Correlations with %N, %C, C/N, and the other isotope accounted for 80 % of variance for δ 15N and 38 % of variance for δ 13C, reflecting N and C losses.more » In contrast, correlations with depth and topography (hummock or hollow) reflected peatland successional history and climate. Higher δ 15N in plots closer to uplands may reflect upland-derived DON inputs and accompanying shifts in N dynamics in the lagg drainage area surrounding the bog. The Suess effect (declining δ 13CO 2 since the Industrial Revolution) lowered δ 13C in recent surficial samples. High δ 15N from –35 to –5 cm probably indicated the depth of ectomycorrhizal activity after tree colonization of the peatland over the last 400 years, as confirmed by the occasional presence of wood down to –35 cm depth. High δ 13C at ~4000 years BP (–65 to –105 cm) could reflect a transition at that time to slower rates of peat accumulation, when 13C discrimination during peat decomposition may increase in importance. Low δ 13C and high δ 15N at –213 and –225 cm (~8500 years BP) corresponded to a warm period during a sedge-dominated rich fen stage. As a result, the above processes appear to be the primary drivers of the observed isotopic patterns, whereas there was no clear evidence for methane dynamics influencing δ 13C patterns.« less

Analysing the isotopic life history of the alpine ungulates Capra ibex and Rupicapra rupicapra rupicapra through their horns.

PubMed

Barbosa, Inês C R; Kley, Maximiliane; Schäufele, Rudi; Auerswald, Karl; Schröder, Wolf; Filli, Flurin; Hertwig, Stefan; Schnyder, Hans

2009-08-01

The horn of ungulate grazers offers a valuable isotopic record of their diet and environment. However, there have been no reports of the spatio-temporal variation of the isotopic composition of horns. We investigated patterns of carbon (delta(13)C) and nitrogen (delta(15)N) isotopic composition along and perpendicular to the horn axis in Capra ibex and Rupicapra rupicapra rupicapra to assess the effects of animal age, within-year (seasonal) and inter-annual variation, natural contamination and sampling position on horn isotope composition. Horns of male C. ibex (n = 23) and R. r. rupicapra (n = 1) were sampled longitudinally on the front (only R. r. rupicapra) and back side and on the surface and sub-surface. The sides of the R. r. rupicapra horn did not differ in delta(13)C. In both species, the horn surface had a 0.15 per thousand lower delta(13)C and a higher carbon-to-nitrogen (C/N) ratio than the sub-surface. Washing the horn with water and organic solvents removed material that caused these differences. With age, the delta(15)N of C. ibex horns increased (+0.1 per thousand year(-1)), C/N ratio increased, and (13)C discrimination relative to atmospheric CO(2) ((13)Delta) increased slightly (+0.03 per thousand year(-1)). Geostatistical analysis of one C. ibex horn revealed systematic patterns of inter-annual and seasonal (13)C changes, but (15)N changed only seasonally. The work demonstrates that isotopic signals in horns are influenced by natural contamination (delta(13)C), age effects ((13)Delta and delta(15)N), and seasonal (delta(13)C and delta(15)N) and inter-annual variation (delta(13)C). The methods presented allow us to distinguish between these effects and thus allow the use of horns as isotopic archives of the ecology of these species and their habitat. Copyright (c) 2009 John Wiley & Sons, Ltd.

Assessment of the LV-C2 Stack Sampling Probe Location for Compliance with ANSI/HPS N13.1-1999

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

Glissmeyer, John A.; Antonio, Ernest J.; Flaherty, Julia E.

2015-09-01

This document reports on a series of tests conducted to assess the proposed air sampling location for the Hanford Tank Waste Treatment and Immobilization Plant (WTP) Low-Activity Waste (LAW) C2V (LV-C2) exhaust stack with respect to the applicable criteria regarding the placement of an air sampling probe. Federal regulations require that a sampling probe be located in the exhaust stack according to the criteria established by the American National Standards Institute/Health Physics Society (ANSI/HPS) N13.1-1999, Sampling and Monitoring Releases of Airborne Radioactive Substances from the Stack and Ducts of Nuclear Facilities. These criteria address the capability of the sampling probemore » to extract a sample that represents the effluent stream. The tests were conducted on the LV-C2 scale model system. Based on the scale model tests, the location proposed for the air sampling probe in the scale model stack meets the requirements of the ANSI/HPS N13.1-1999 standard for velocity uniformity, flow angle, gas tracer and particle tracer uniformity. Additional velocity uniformity and flow angle tests on the actual stack will be necessary during cold startup to confirm the validity of the scale model results in representing the actual stack.« less

The effects of isotope-labeled analogs on the LC-IDMS measurement by comparison of ESI responses and matrix effect of melamine, 13C3-melamine, 13C3+15N3-melamine, and 15N3-melamine.

PubMed

Li, Xiu Qin; Zhang, Qing He; Yang, Zong; Li, Hong Mei; Huang, Dong Feng

2017-05-01

In this paper, the effect of isotope-labeled analogs on the liquid chromatography-isotope dilution mass spectrometry (LC-IDMS) measurement was evaluated based on the comparison research of electrospray ionization responses (ESI) and matrix effect of melamine, 13 C 3 -melamine, 13 C 3 + 15 N 3 -melamine, and 15 N 3 -melamine. The isotope-labeled melamines had similar ionization efficiency with melamine in the electrospray ionization source, but the intensity of corresponding quantitative fragment ions had distinctive differences. Based on the density functional theory at the B3LYP/6-311+G** level, this phenomenon was explained very well. The rare cleavage pathways of melamine, which just could be exactly identified by 15 N-labeled melamines, resulted in the difference of quantitative fragment ions between 15 N-labeled melamines and melamine. The interaction of ESI response between melamine and isotope-labeled melamines was investigated using MRM monitor mode. 15 N-labeled melamine had significant ion inter-suppression effect on melamine, while 13 C-labeled melamine had little influence on melamine. Finally, the influence of different isotope-labeled melamines on the LC-IDMS result was evaluated using the IDMS correction factor (θ). Taking the determination of melamine in milk powder as an example, the matrix effects of different isotope-labeled melamines and melamine had notable difference and the impact of this difference on the measurement results depended on the concentrations of analyte and matrix solution. It was worth noting that 15 N 3 -melamine exhibited significant ion suppression to melamine in matrix solution. The deviation of the results from IDMS method might reach 59% using 15 N 3 -melamine as internal standard in special matrix solution. Graphical Abstract The comparison of ESI responses of melamine, 13 C 3 -melamine, 13 C 3 + 15 N 3 -melamine and 15 N 3 -melamine.

Variation in hair δ13C and δ15N values in long-tailed macaques (Macaca fascicularis) from Singapore

USGS Publications Warehouse

Schillaci, Michael A.; Castellini, J. Margaret; Stricker, Craig A.; Jones-Engel, Lisa; Lee, Benjamin P.Y.-H.

2014-01-01

Much of the primatology literature on stable isotope ratios of carbon (δ13C) and nitrogen (δ15N) has focused on African and New World species, with comparatively little research published on Asian primates. Here we present hair δ13C and δ15N isotope values for a sample of 33 long-tailed macaques from Singapore. We evaluate the suggestion by a previous researcher that forest degradation and biodiversity loss in Singapore have led to a decline in macaque trophic level. The results of our analysis indicated significant spatial variability in δ13C but not δ15N. The range of variation in δ13C was consistent with a diet based on C3 resources, with one group exhibiting low values consistent with a closed canopy environment. Relative to other macaque species from Europe and Asia, the macaques from Singapore exhibited a low mean δ13C value but mid-range mean δ15N value. Previous research suggesting a decline in macaque trophic level is not supported by the results of our study.

The response of the foliar antioxidant system and stable isotopes (δ(13)C and δ(15)N) of white willow to low-level air pollution.

PubMed

Wuytack, Tatiana; AbdElgawad, Hamada; Staelens, Jeroen; Asard, Han; Boeckx, Pascal; Verheyen, Kris; Samson, Roeland

2013-06-01

In this study we aimed to determine and elucidate the effect of ambient air pollution on the foliar antioxidant system and stable carbon and nitrogen isotopes of white willow (Salix alba L.). We grew white willow in uniform potting soil in the near vicinity of sixteen air quality monitoring stations in Belgium where nitrogen dioxide (NO2), ozone, sulfur dioxide and particulate matter concentrations were continuously measured. The trees were exposed to ambient air during six months (April-September 2011), and, thereafter, the degree of lipid peroxidation and foliar content of antioxidant molecules (ascorbate, glutathione, polyphenols, flavonoids), antioxidant enzymes (superoxide dismutase, ascorbate peroxidase, peroxidase) and foliar stable carbon (δ(13)C) and nitrogen (δ(15)N) isotopes were measured. We found that lipid peroxidation was caused by air pollution stress, arising from high ambient NO2 concentrations, as shown by an increased amount of malondialdehyde. The antioxidant system was activated by increasing the amount of polyphenols at monitoring stations with a high atmospheric NO2 and low O3 concentration, while no increase of key enzymes (e.g., ascorbate, glutathione) was observed. The δ(13)C also decreased with increasing NO2 concentrations and decreasing O3 concentrations, probably reflecting a decreased net photosynthesis and/or a concomitant decrease of (13)CO2 in the atmosphere. Shade also influenced foliar δ(13)C and the content of leaf ascorbate and glutathione. Copyright © 2013 Elsevier Masson SAS. All rights reserved.

Afforestation impacts microbial biomass and its natural (13)C and (15)N abundance in soil aggregates in central China.

PubMed

Wu, Junjun; Zhang, Qian; Yang, Fan; Lei, Yao; Zhang, Quanfa; Cheng, Xiaoli

2016-10-15

We investigated soil microbial biomass and its natural abundance of δ(13)C and δ(15)N in aggregates (>2000μm, 250-2000μm, 53-250μm and <53μm) of afforested (implementing woodland and shrubland plantations) soils, adjacent croplands and open area (i.e., control) in the Danjiangkou Reservoir area of central China. The afforested soils averaged higher microbial biomass carbon (MBC) and nitrogen (MBN) levels in all aggregates than in open area and cropland, with higher microbial biomass in micro-aggregates (<250μm) than in macro-aggregates (>2000μm). The δ(13)C of soil microbial biomass was more enriched in woodland soils than in other land use types, while δ(15)N of soil microbial biomass was more enriched compared with that of organic soil in all land use types. The δ(13)C and δ(15)N of microbial biomass were positively correlated with the δ(13)C and δ(15)N of organic soil across aggregates and land use types, whereas the (13)C and (15)N enrichment of microbial biomass exhibited linear decreases with the corresponding C:N ratio of organic soil. Our results suggest that shifts in the natural (13)C and (15)N abundance of microbial biomass reflect changes in the stabilization and turnover of soil organic matter (SOM) and thereby imply that afforestation can greatly impact SOM accumulation over the long-term. Copyright © 2016 Elsevier B.V. All rights reserved.

On the problem of resonance assignments in solid state NMR of uniformly 15N, 13C-labeled proteins

NASA Astrophysics Data System (ADS)

Tycko, Robert

2015-04-01

Determination of accurate resonance assignments from multidimensional chemical shift correlation spectra is one of the major problems in biomolecular solid state NMR, particularly for relative large proteins with less-than-ideal NMR linewidths. This article investigates the difficulty of resonance assignment, using a computational Monte Carlo/simulated annealing (MCSA) algorithm to search for assignments from artificial three-dimensional spectra that are constructed from the reported isotropic 15N and 13C chemical shifts of two proteins whose structures have been determined by solution NMR methods. The results demonstrate how assignment simulations can provide new insights into factors that affect the assignment process, which can then help guide the design of experimental strategies. Specifically, simulations are performed for the catalytic domain of SrtC (147 residues, primarily β-sheet secondary structure) and the N-terminal domain of MLKL (166 residues, primarily α-helical secondary structure). Assuming unambiguous residue-type assignments and four ideal three-dimensional data sets (NCACX, NCOCX, CONCA, and CANCA), uncertainties in chemical shifts must be less than 0.4 ppm for assignments for SrtC to be unique, and less than 0.2 ppm for MLKL. Eliminating CANCA data has no significant effect, but additionally eliminating CONCA data leads to more stringent requirements for chemical shift precision. Introducing moderate ambiguities in residue-type assignments does not have a significant effect.

Accounting for the effects of lipids in stable isotope (δ13C and δ15N values) analysis of skin and blubber of balaenopterid whales.

PubMed

Ryan, Conor; McHugh, Brendan; Trueman, Clive N; Harrod, Chris; Berrow, Simon D; O'Connor, Ian

2012-12-15

Stable isotope values (δ(13)C and δ(15)N) of darted skin and blubber biopsies can shed light on habitat use and diet of cetaceans, which are otherwise difficult to study. Non-dietary factors affect isotopic variability, chiefly the depletion of (13)C due to the presence of (12)C-rich lipids. The efficacy of post hoc lipid-correction models (normalization) must be tested. For tissues with high natural lipid content (e.g., whale skin and blubber), chemical lipid extraction or normalization is necessary. C:N ratios, δ(13)C values and δ(15)N values were determined for duplicate control and lipid-extracted skin and blubber of fin (Balaenoptera physalus), humpback (Megaptera novaeangliae) and minke whales (B. acutorostrata) by continuous-flow elemental analysis isotope ratio mass spectrometry (CF-EA-IRMS). Six different normalization models were tested to correct δ(13)C values for the presence of lipids. Following lipid extraction, significant increases in δ(13)C values were observed for both tissues in the three species. Significant increases were also found for δ(15)N values in minke whale skin and fin whale blubber. In fin whale skin, the δ(15)N values decreased, with no change observed in humpback whale skin. Non-linear models generally out-performed linear models and the suitability of models varied by species and tissue, indicating the need for high model specificity, even among these closely related taxa. Given the poor predictive power of the models to estimate lipid-free δ(13)C values, and the unpredictable changes in δ(15)N values due to lipid-extraction, we recommend against arithmetical normalization in accounting for lipid effects on δ(13)C values for balaenopterid skin or blubber samples. Rather, we recommend that duplicate analysis of lipid-extracted (δ(13)C values) and non-treated tissues (δ(15)N values) be used. Copyright © 2012 John Wiley & Sons, Ltd.

13C and 15N—Chemical Shift Anisotropy of Ampicillin and Penicillin-V Studied by 2D-PASS and CP/MAS NMR

NASA Astrophysics Data System (ADS)

Antzutkin, Oleg N.; Lee, Young K.; Levitt, Malcolm H.

1998-11-01

The principal values of the chemical shift tensors of all13C and15N sites in two antibiotics, ampicillin and penicillin-V, were determined by 2-dimensionalphaseadjustedspinningsideband (2D-PASS) and conventional CP/MAS experiments. The13C and15N chemical shift anisotropies (CSA), and their confidence limits, were evaluated using a Mathematica program. The CSA values suggest a revised assignment of the 2-methyl13C sites in the case of ampicillin. We speculate on a relationship between the chemical shift principal values of many of the13C and15N sites and the β-lactam ring conformation.

Stable isotope ratios of carbon and nitrogen and mercury concentrations in 13 toothed whale species taken from the western Pacific Ocean off Japan.

PubMed

Endo, Tetsuya; Hisamichi, Yohsuke; Kimura, Osamu; Haraguchi, Koichi; Lavery, Shane; Dalebout, Merel L; Funahashi, Naoko; Baker, C Scott

2010-04-01

Stable isotope ratios of carbon (partial differential(13)C) and nitrogen (partial differential(15)N) and total mercury (T-Hg) concentrations were measured in red meat samples from 11 odontocete species (toothed whales, dolphins, and porpoises) sold in Japan (n = 96) and in muscle samples from stranded killer whales (n = 6) and melon-headed whales (n = 15), and the analytical data for these species were classified into three regions (northern, central, and southern Japan) depending on the locations in which they were caught or stranded. The partial differential(15)N in the samples from southern Japan tended to be lower than that in samples from the north, whereas both partial differential(13)C and T-Hg concentrations in samples from the south tended to higher than those in samples from northern Japan. Negative correlations were found between the partial differential(13)C and partial differential(15)N values and between the partial differential(15)N value and T-Hg concentrations in the combined samples all three regions (gamma= -0.238, n = 117, P < 0.01). The partial differential(13)C, partial differential(15)N, and T-Hg concentrations in the samples varied more by habitat than by species. Spatial variations in partial differential(13)C, partial differential(15)N, and T-Hg concentrations in the ocean may be the cause of these phenomena.

Determination of agmatine using isotope dilution UPLC-tandem mass spectrometry: application to the characterization of the arginine decarboxylase pathway in Pseudomonas aeruginosa.

PubMed

Dalluge, Joseph J; McCurtain, Jennifer L; Gilbertsen, Adam J; Kalstabakken, Kyle A; Williams, Bryan J

2015-07-01

A method has been developed for the direct determination of agmatine in bacterial culture supernatants using isotope dilution ultra performance liquid chromatography (UPLC)-tandem mass spectrometry (UPLC-MS/MS). Agmatine determination in bacterial supernatants is comprised of spiking culture or isolate supernatants with a fixed concentration of uniformly labeled (13)C5,(15)N4-agmatine (synthesized by decarboxylation of uniformly labeled (13)C6,(15)N4-arginine using arginine decarboxylase from Pseudomonas aeruginosa) as an internal standard, followed by derivatization with 4-fluoro-7-nitro-2,1,3-benzoxadiazole (NBDF) to improve the reversed-phase chromatographic retention characteristics of agmatine, as well as the selectivity and sensitivity of UPLC-MS/MS detection of this amine in complex biologically derived mixtures. Intrasample precisions for measurement of agmatine in culture supernatants average 4.1% (relative standard deviation). Calibration curves are linear over the range 5 nM to 10 μM, and the detection limit is estimated at 1.5 nM. To demonstrate the utility of the method, agmatine levels in supernatants of overnight cultures of wild-type (UCBPP-PA14), as well as arginine decarboxylase and agmatine deiminase mutant strains of P. aeruginosa strain UCBPP-PA14 were measured. This method verified that the mutant strains are lacking the specific metabolic capabilities to produce and metabolize agmatine. In addition, measurement of agmatine in supernatants of a panel of clinical isolates from patients with cystic fibrosis revealed that three of the P. aeruginosa isolates hyper-secreted agmatine into the supernatant, hypothesized to be a result of a mutation in the aguA gene. Because agmatine has potential inflammatory activities in the lung, this phenotype may be a virulence factor for P. aeruginosa in the lung environment of cystic fibrosis patients.

Determination of agmatine using isotope dilution UPLC-tandem mass spectrometry: application to the characterization of the arginine decarboxylase pathway in Pseudomonas aeruginosa

PubMed Central

McCurtain, Jennifer L.; Gilbertsen, Adam J.; Kalstabakken, Kyle A.; Williams, Bryan J.

2018-01-01

A method has been developed for the direct determination of agmatine in bacterial culture supernatants using isotope dilution ultra performance liquid chromatography (UPLC)-tandem mass spectrometry (UPLC-MS/MS). Agmatine determination in bacterial supernatants is comprised of spiking culture or isolate supernatants with a fixed concentration of uniformly labeled 13C5,15N4-agmatine (synthesized by decarboxylation of uniformly labeled 13C6,15N4-arginine using arginine decarboxylase from Pseudomonas aeruginosa) as an internal standard, followed by derivatization with 4-fluoro-7-nitro-2,l,3-benzoxadiazole (NBDF) to improve the reversed-phase chromatographic retention characteristics of agmatine, as well as the selectivity and sensitivity of UPLC-MS/MS detection of this amine in complex biologically derived mixtures. Intrasample precisions for measurement of agmatine in culture supernatants average 4.1 % (relative standard deviation). Calibration curves are linear over the range 5 nM to 10 μM, and the detection limit is estimated at 1.5 nM. To demonstrate the utility of the method, agmatine levels in supernatants of overnight cultures of wild-type (UCBPP-PA14), as well as arginine decarboxylase and agmatine deiminase mutant strains of P. aeruginosa strain UCBPP-PA14 were measured. This method verified that the mutant strains are lacking the specific metabolic capabilities to produce and metabolize agmatine. In addition, measurement of agmatine in supernatants of a panel of clinical isolates from patients with cystic fibrosis revealed that three of the P. aeruginosa isolates hyper-secreted agmatine into the supernatant, hypothesized to be a result of a mutation in the aguA gene. Because agmatine has potential inflammatory activities in the lung, this phenotype may be a virulence factor for P. aeruginosa in the lung environment of cystic fibrosis patients. PMID:25957842

Shemya AFB, Alaska Revised Uniform Summary of Surface Weather Observations (RUSSWO). Parts A-F.

DTIC Science & Technology

1984-05-01

34.40 41 -0 4S-53 36 % WIND oil . SPEED SSE 1 ____ .7 ~~* iSE~* -E.* 16.. SSW7.,1 19.S mw c .373 17*4 1, VASIL 1.4 TOTAL HUMUS OF OILSERVATIOI4S USAFETAC 0...STATIC’K TAUT OUTS 16 cO " MISI 4I ION. SPEED .FMEAN (KNTS) 1.3 4.6 7.10 11-16 17.-21 22.27 282 33 34.40 41.0 46.5 t5 WN oil . SPUD__ ____ N .. 1 ____ NNE...p WET BULB TEMPERATURE DEPRESSION (F) TOTAL TOTAL (F) 12 3-4 5- 7.8 9. 10 11112,13.14 15-16 17- 14 19.20 21.22122.2425.2 27.229.30 - .1 Oil °II Wei

Following isotopes in pulse-chase enriched aspen seedlings

NASA Astrophysics Data System (ADS)

Norris, C. E.; Wasylishen, R. E.; Landhäusser, S.; Quideau, S. A.

2011-12-01

One method to quantitatively trace biogeochemical fluxes through ecosystems, such as organic matter decomposition, is to use plant material enriched with stable isotopes. However, as plant macromolecules are known to vary in their rate of formation and decomposition, both the enrichment levels and the location of enrichment within the plant material should be characterized prior to decomposition and tracing studies. Aspen (Populus tremuloides Michx.) is a common tree species with a diverse organic matter chemical structure found in the western Canadian boreal forest. This study used a multi pulse and multi chase enrichment of stable isotopes (15N and 13C) on aspen seedlings to determine the seedling enrichment, isotope movement among plant tissues and translocation of isotopes within plant macromolecules e.g., carbohydrates and lignin. As expected, all tissues experienced increased enrichment with multiple pulses. An initial enrichment with 13C was observed in the leaves followed by translocation to the stems and roots while the 15N moved upward from the roots to leaves. The macromolecular chemistry of the organic carbon was further characterized using 13C solid state nuclear magnetic resonance spectroscopy. After the initial two hour chase period enrichment of the O-alkyl type (carbohydrate) carbon within the leaves was identified, followed by redistribution to more complex carbon compounds after the one week chase period. Root and stem tissues did not show the same pattern. Rather, changes in 13C enrichment were observed in shifting ethyl and methyl alkyl (lipid) carbon peak intensities for the stem samples while roots did not preferentially allocate 13C to a specific macromolecule. These results confirm that stable isotope enrichment of plants was non-uniform across macromolecules and tissue types. Enrichment of aspen seedlings was therefore dependant on the pulse-chase sequence used.

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.

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

NASA Technical Reports Server (NTRS)

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

1985-01-01

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

Determination of δ13C, δ15N, or δ34S by isotope-ratio-monitoring mass spectrometry using an elemental analyzer

USGS Publications Warehouse

Johnson, Craig A.; Stricker, Craig A.; Gulbransen, Cayce A.; Emmons, Matthew P.

2018-02-14

This report describes procedures used in the Geology, Geophysics, and Geochemistry Science Center of the U.S. Geological Survey in Denver, Colorado, to determine the stable-isotope ratios 13C/12C, 15N/14N, and 34S/32S in solid materials. The procedures use elemental analyzers connected directly to gas-source isotope-ratio mass spectrometers. A different elemental–analyzer–mass-spectrometer system is used for 13C/12C and 15N/14N than is used for 34S/32S to accommodate differences in reagents, catalysts, and instrument settings.

High-resolution molecular structure of a peptide in an amyloid fibril determined by magic angle spinning NMR spectroscopy

NASA Astrophysics Data System (ADS)

Jaroniec, Christopher P.; Macphee, Cait E.; Bajaj, Vikram S.; McMahon, Michael T.; Dobson, Christopher M.; Griffin, Robert G.

2004-01-01

Amyloid fibrils are self-assembled filamentous structures associated with protein deposition conditions including Alzheimer's disease and the transmissible spongiform encephalopathies. Despite the immense medical importance of amyloid fibrils, no atomic-resolution structures are available for these materials, because the intact fibrils are insoluble and do not form diffraction-quality 3D crystals. Here we report the high-resolution structure of a peptide fragment of the amyloidogenic protein transthyretin, TTR(105-115), in its fibrillar form, determined by magic angle spinning NMR spectroscopy. The structure resolves not only the backbone fold but also the precise conformation of the side chains. Nearly complete 13C and 15N resonance assignments for TTR(105-115) formed the basis for the extraction of a set of distance and dihedral angle restraints. A total of 76 self-consistent experimental measurements, including 41 restraints on 19 backbone dihedral angles and 35 13C-15N distances between 3 and 6 Å were obtained from 2D and 3D NMR spectra recorded on three fibril samples uniformly 13C, 15N-labeled in consecutive stretches of four amino acids and used to calculate an ensemble of peptide structures. Our results indicate that TTR(105-115) adopts an extended -strand conformation in the amyloid fibrils such that both the main- and side-chain torsion angles are close to their optimal values. Moreover, the structure of this peptide in the fibrillar form has a degree of long-range order that is generally associated only with crystalline materials. These findings provide an explanation of the unusual stability and characteristic properties of this form of polypeptide assembly.

Bacterial Expression and Purification of the Amyloidogenic Peptide PAPf39 for Multidimensional NMR Spectroscopy

PubMed Central

Shanmuganathan, Aranganathan; Bishop, Anthony C.; French, Kinsley C.; McCallum, Scott A.; Makhatadze, George I.

2013-01-01

PAPf39 is a 39 residue peptide fragment from human prostatic acidic phosphatase that forms amyloid fibrils in semen. These fibrils have been implicated in facilitating HIV transmission. To enable structural studies of PAPf39 by NMR spectroscopy, efficient methods allowing the production of milligram quantities of isotopically labeled peptide are essential. Here, we report the high-yield expression, as a fusion to ubiquitin at the N-terminus and an intein at the C-terminus, and purification of uniformly labeled 13C- and 15N-labeled PAPf39 peptide. This allows the study of the PAPf39 monomer conformational ensemble by NMR spectroscopy. To this end, we performed the NMR chemical shift assignment of the PAPf39 peptide in the monomeric state at low pH. PMID:23314347

Using isotopic patterns of ectomycorrhizal and saprotrophic fungi to elucidate fungal sources of carbon and nitrogen in a Norway spruce stand

NASA Astrophysics Data System (ADS)

Chen, Janet; Rinne-Garmston, Katja; Penttilä, Reijo; Hobbie, Erik; Mäkipää, Raisa

2016-04-01

To predict effects of global change on fungal community structure and the consequential effects on carbon (C) and nitrogen (N) cycling, we first need to understand different fungal sources of C and N. We determined sources of C and N by measuring δ15N and δ13C of an extensive collection of ectomycorrhizal and saprotrophic sporocarps and their potential substrates from Norway spruce (Picea abies) stands in southern Finland. The substrates included organic soil, roots in organic soil, mineral soil, roots in mineral soil, moss, needles, needles in litter, branches, twigs in litter, wood and decay wood from stages I-V. Notably, δ15N and δ13C analysis of wood in decay stages I-V was a novel measurement, as were our associations between wood decay fungi and the decay stage of trees. Decay stage of wood significantly correlated with the δ15N and δ13C of associated saprotrophic wood decay fungi species. Fungi were lower in δ15N by 0.3-0.7‰ when associated with decay wood in stages II and III compared to I and IV and higher in δ13C by 0.9-1.2‰ when associated with decay stage I compared to decay stages II-IV. The ectomycorrhizal fungi, Piloderma fallax, was significantly correlated with 15N enrichment of decay wood upon its introduction in decay stages III and IV that continued to the later decay stage V, with δ15N of decay stage V 1.5‰ higher than decay stage IV. These results indicate that wood decay fungi rely on C and N from various wood decay stages and influence C and N pools of wood as well. Litter decay fungi were lower in δ13C than wood decay fungi by 1.9‰ and higher in δ15N by 3‰ and isotopically tracked their C and N sources. Calocera viscosa, Gymnopus acervatus, and Leotia lubrica were highly 15N-enriched compared to other saprotrophic fungi and they had δ15N values similar to fungi with hydrophobic ectomycorrhizae indicating function more similar to ectomycorrhizal fungi or N sources similar to this functional group. Similar to other studies, ectomycorrhizal fungi were 15N-enriched relative to saprotrophic fungi and fungi with hydrophobic ectomycorrhizae were 15N-enriched compared to fungi with hydrophilic ectomycorrhizae by 3.6‰. δ15N and δ13C values indicate that ectomycorrhizal fungi derive C from plant sugars similar to woody substrate, and acquire N from older sources within the litter layer and deeper in organic and mineral soils, with hydrophobic ectomycorrhizae using older sources of N than hydrophilic ectomycorrhizae. Interestingly, Entoloma cetratum with hydrophilic ectomycorrhizae and Hydnum repandum with hydrophobic ectomycorrhizae both had abnormally high δ15N values that suggest an irregular 15N-enriched source of N, likely from a higher 15N-enriched trophic level.

Stable isotope ratios as indicators of trophic status: Uncertainties imposed by geographic effects

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

Schell, D.M.

1995-12-31

Isotope ratios of carbon and nitrogen are often suggested as indicators to determine trophic status and carbon sources of marine organisms in explaining relative concentrations of pollutants. Whereas this technique is effective with organisms resident in ecosystems having homogeneous primary productivity regimes and uniform isotope ratios in the productivity base, it often is confounded by migratory movements by larger organisms across isotopic gradients. Tissues containing a temporal record such as baleen plates or whiskers show these effects clearly. Bowhead whales in Alaskan waters seasonally move across carbon isotope gradients of 5{per_thousand} in zooplankton and reflect these differences in the keratinmore » of baleen plates and in overall body composition. However, no significant differences in {delta}{sup 15}N are evident regionally in northern Alaskan zooplankton. In contrast, the Southern Ocean is characterized by extreme latitudinal gradients in both {delta}{sup 13}C and {delta}{sup 15}N with the most pronounced effects occurring at the subtropical convergence. Prey taken by marine mammals south of this zone are depleted in both {sup 15}N and {sup 13}C by up to 8{per_thousand}. Data on southern right whales (Eubalaena glacialis), Bryde`s whale (Balaenoptera edenl), pygmy right whales (Caperea marginate) and antarctic fur seal (Arctocephalos gazella) show the effects of migratory movements across the gradient in both carbon and nitrogen isotope ratios. Similar patterns in marine mammal tissues from Australia, South Africa and South America indicate that the observed patterns are circumpolar. Within a given region, trophic effects shift {delta}{sup 15}N values consistent with observed feeding habits.« less

7Li(15N, 14C)8Be reaction at 81 MeV and 14C + 8Be interaction versus that of 13C + 8Be

NASA Astrophysics Data System (ADS)

Rudchik, A. T.; Rudchik, A. A.; Muravynets, L. M.; Kemper, K. W.; Rusek, K.; Koshchy, E. I.; Piasecki, E.; Trzcinska, A.; Pirnak, Val. M.; Ponkratenko, O. A.; Strojek, I.; Stolarz, A.; Plujko, V. A.; Sakuta, S. B.; Siudak, R.; Ilyin, A. P.; Stepanenko, Yu. M.; Shyrma, Yu. O.; Uleshchenko, V. V.

2018-03-01

Angular distributions of the 7Li(15N, 14C)8Be reaction were measured at the energy Elab(15N) = 81 MeV. Data for transfer to the ground and first two excited states in 8Be were acquired as well as to the 14C ground and excited states. The reaction data were analyzed within the coupled-reaction-channels (CRC) method. The required 15N + 7Li entrance channel potential was taken from the 15N + 7Li elastic scattering. The 14C + 8Be potential was found by fitting Woods-Saxon form potentials to those generated by double folded real and imaginary potentials in the region of interaction. These generated potentials were then used in the CRC calculations. Proton transfer dominants this reaction, including to the excited states of 8Be. The reaction dependence on the exit channel potential was examined by using the 13C + 8Be potential previously deduced from the 9Be(12C, 13C)8Be reaction and 14C + 8Be from the 13C(9Be, 8Be)14C reaction.

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

PubMed

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

2016-07-01

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

Isotopic ecology of coyotes from scat and road kill carcasses: A complementary approach to feeding experiments

PubMed Central

Koch, Paul L.

2017-01-01

Scat is frequently used to study animal diets because it is easy to find and collect, but one concern is that gross fecal analysis (GFA) techniques exaggerate the importance of small-bodied prey to mammalian mesopredator diets. To capitalize on the benefits of scat, we suggest the analysis of scat carbon and nitrogen isotope values (δ13C and δ15N). This technique offers researchers a non-invasive method to gather short-term dietary information. We conducted three interrelated studies to validate the use of isotopic values from coyote scat: 1) we determined tissue-to-tissue apparent C and N isotope enrichment factors (ε13* and ε15*) for coyotes from road kill animals (n = 4); 2) we derived diet-to-scat isotope discrimination factors for coyotes; and 3) we used field collected coyote scats (n = 12) to compare estimates of coyote dietary proportions from stable isotope mixing models with estimates from two GFA techniques. Scat consistently had the lowest δ13C and δ15N values among the tissues sampled. We derived a diet-to-scat Δ13C value of -1.5‰ ± 1.6‰ and Δ15N value of 2.3‰ ± 1.3‰ for coyotes. Coyote scat δ13C and δ15N values adjusted for discrimination consistently plot within the isotopic mixing space created by known dietary items. In comparison with GFA results, we found that mixing model estimates of coyote dietary proportions de-emphasize the importance of small-bodied prey. Coyote scat δ13C and δ15N values therefore offer a relatively quick and non-invasive way to gain accurate dietary information. PMID:28369133

Isotopic ecology of coyotes from scat and road kill carcasses: A complementary approach to feeding experiments.

PubMed

Reid, Rachel E B; Koch, Paul L

2017-01-01

Scat is frequently used to study animal diets because it is easy to find and collect, but one concern is that gross fecal analysis (GFA) techniques exaggerate the importance of small-bodied prey to mammalian mesopredator diets. To capitalize on the benefits of scat, we suggest the analysis of scat carbon and nitrogen isotope values (δ13C and δ15N). This technique offers researchers a non-invasive method to gather short-term dietary information. We conducted three interrelated studies to validate the use of isotopic values from coyote scat: 1) we determined tissue-to-tissue apparent C and N isotope enrichment factors (ε13* and ε15*) for coyotes from road kill animals (n = 4); 2) we derived diet-to-scat isotope discrimination factors for coyotes; and 3) we used field collected coyote scats (n = 12) to compare estimates of coyote dietary proportions from stable isotope mixing models with estimates from two GFA techniques. Scat consistently had the lowest δ13C and δ15N values among the tissues sampled. We derived a diet-to-scat Δ13C value of -1.5‰ ± 1.6‰ and Δ15N value of 2.3‰ ± 1.3‰ for coyotes. Coyote scat δ13C and δ15N values adjusted for discrimination consistently plot within the isotopic mixing space created by known dietary items. In comparison with GFA results, we found that mixing model estimates of coyote dietary proportions de-emphasize the importance of small-bodied prey. Coyote scat δ13C and δ15N values therefore offer a relatively quick and non-invasive way to gain accurate dietary information.

Use of stable isotopes to identify dietary differences across subpopulations and sex for a free-ranging generalist herbivore.

PubMed

Walter, W David

2014-01-01

Carbon and nitrogen isotopes in tissues can be used to understand plants consumed by various taxa, but can they provide additional information about consumers? Values of δ(13)C and δ(15)N were assessed from tissue of free-ranging elk (Cervus elaphus) occupying disparate habitats of mixed prairie-oak savannah that contained C3 agricultural crops in a C4-dominated landscape and in key plants consumed by elk. Muscle and hoof samples were collected from female and male elk in two subpopulations (forested land and grassland) from private land and one subpopulation from the Wichita Mountains Wildlife Refuge (refuge) in 2001-2006. Previous research identified differences between mean muscle δ(13)C and δ(15)N and mean hoof δ(13)C and δ(15)N indicating that isotopes differed between tissues of varying metabolic activity. Mean δ(13)C in hoof of elk on forested land and grassland were lower than hoof δ(13)C from elk in the refuge indicating greater long-term consumption of C3 plants by elk on forested land and grassland subpopulations. The δ(15)N in hoof was greater for elk outside the refuge than that for elk in the refuge. Interaction of sex and subpopulation only occurred for hoof δ(15)N suggesting that factors such as tissue type, sex, and habitat need to be considered to understand free-ranging ecology of generalist herbivores using stable isotopes. Availability of C3 agricultural crops high in percent nitrogen on a nearly annual basis in a C4-dominated landscape was likely driving differences in tissue δ(13)C and δ(15)N among subpopulations of free-ranging elk. An increase in tissue δ(15)N resulted from an increase in the consumption of higher δ(15)N in forage for sexes and subpopulations of a free-ranging ungulate in North America but δ(15)N should be further evaluated as an index of nutrition for subpopulations of generalist herbivores.

Reciprocal trade of Carbon and Nitrogen at the root-fungus interface in ectomycorrhizal beech plants

NASA Astrophysics Data System (ADS)

Kaiser, Christina; Mayerhofer, Werner; Dietrich, Marlies; Gorka, Stefan; Schintlmeister, Arno; Reipert, Siegfried; Schweiger, Peter; Weidinger, Marieluise; Wiesenbauer, Julia; Martin, Victoria; Richter, Andreas; Woebken, Dagmar

2017-04-01

Plants deliver recently assimilated carbon (C) to mycorrhizal fungi, and receive nutrients, such as N and P, in exchange. A reciprocal exchange of C and nutrients between plants and mycorrhizal fungi (i.e., fungi which deliver more nutrients receive more plant C in return and vice versa) has been suggested for arbuscular mycorrhizal symbioses by some studies, but challenged by others. For ectomycorrhizal associations even less is known on how the exchange of C for nutrients is regulated, and whether it is based on reciprocity, or other controls. The aim of this study was to test the concept of reciprocal rewards between beech (Fagus sylvatica) and their associated ectomycorrhizal fungi on different scales, namely (a) across associations between individual root tips of beech and different fungal partners, and (b) at the subcellular scale at the plant-fungus interface. We exposed young beech trees associated with natural mycorrhizal fungal communities to a 13CO2 atmosphere and added 15N-labelled amino acids to a 'litter compartment', that mycorrhizal hyphae, but not plant roots could access. Plants were harvested within 2 days after application of 15N and less than one day after applying 13CO2. If the trading of C for N was reciprocal, we expect that 13C would be correlated to 15N across individual plant-fungal connections and at the subcellular scale within one mycorrhizal root tip, respectively. We collected individual mycorrhizal root-tips from 8 plants right after harvest, analyzed their 13C and 15N content by isotope-ratio mass spectrometry (EA-IRMS) and performed ITS sequencing to identify fungal communities associated with individual root tips. Selected mycorrhizal root tips were also prepared for nano-scale secondary ion mass spectrometry (NanoSIMS) to visualize the spatial distribution of 13C and 15N in cross-sections of mycorrhizal root-tips at the subcellular scale. Our results showed a significant, albeit weak correlation between 13C and 15N across collected mycorrhizal root-tips, the variability of which was seemingly influenced by fungal colonization pattern. Within a cross-section of an individual root-tip, however, NanoSIMS imaging revealed not only a high spatial heterogeneity of 13C and 15N across plant and fungal cells, but also a strong spatial correlation between 13C and 15N in both, plant cells and fungal cells of the Hartig Net, the fungal mantle and external hyphae. Intriguingly, individual 'hotspots' of external fungal hyphae that were highly enriched in 15N (delivering high amounts of the added 15N to the plant), were also always extraordinarily enriched in 13C (receiving more 13C in return). Our results provide first evidence for a reciprocal exchange of C for N between plants and ectomycorrhizal fungi at the subcellular scale. This indicates that a mechanism at the cellular level exists, that (i) either allows plants to direct their C flow into N-delivering parts of the mycorrhizal hyphal network or (ii) allow the fungus to 'draw' more C from the plant (develop a higher sink strength) when it has access to N. While such a mechanism still remains to be elucidated, our study shows, for the first time, direct evidence for its existence.

Single-cell measurement of archaeal and bacterial carbon assimilation in dark Pacific Ocean waters

NASA Astrophysics Data System (ADS)

Dekas, A. E.; Mayali, X.; Parada, A. E.; Fuhrman, J. A.; Weber, P. K.; Pett-Ridge, J.

2016-02-01

Microbial activity in the dark ocean plays a critical role in nutrient and elemental cycling. Here, we investigated the activity of archaea and bacteria on the single-cell level during dark incubations of Pacific Ocean water, and specifically their capacity for chemoautotrophy. Samples were collected 19 km off the coast of Los Angeles, at a depth of 150 m, and off the coast of San Francisco, at the surface. Incubations were amended with isotopically-labeled organic or inorganic carbon (13C-bicarbonate, 15N-amino acids or dual-labeled 13C-15N-amino acids), and uptake was detected using nanoscale secondary ion mass spectrometry (NanoSIMS). We analyzed 4,968 individual cells using an automated NanoSIMS analysis with particle-recognition software. After 7 days, 95% and 89% of cells (deep and shallow, respectively) demonstrated anabolic activity, i.e., incorporation of at least one isotopically-labeled substrate. Chemoautotrophy was detected at both sites, with 36% and 9% of cells (deep and shallow, respectively) assimilating 13C-bicarbonate in the dark. Fluorescence in situ hybridization coupled to NanoSIMS analysis was performed to link 16S rRNA phylogeny to patterns of C-assimilation. Thaumarchaea were found to dominate chemoautotrophy at both sites, with 13C-bicarbonate assimilation in nearly all cells hybridized with the Cren537 probe, but none hybridized with a general bacterial probe (Eub338). Conversely, widespread assimilation of both 15N and 13C from 15N-13C-amino acids was observed in the bacterial assemblage, but not in the Thaumarchaea. Interestingly, Thaumarchaeal cells were enriched in 15N after incubation with 15N-13C-amino acids, but not 13C, suggesting selective N assimilation from amino acids or substrate recycling. Together, our results demonstrate the value of single-cell measurements in characterizing patterns of C metabolism in mixed microbial community, and underscore the importance of Thaumarchaea in marine chemoautotrophy.

Diet-tissue stable isotope (Δ(13)C and Δ(15)N) discrimination factors for multiple tissues from terrestrial reptiles.

PubMed

Steinitz, Ronnie; Lemm, Jeffrey M; Pasachnik, Stesha A; Kurle, Carolyn M

2016-01-15

Stable isotope analysis is a powerful tool for reconstructing trophic interactions to better understand drivers of community ecology. Taxon-specific stable isotope discrimination factors contribute to the best use of this tool. We determined the first Δ(13)C and Δ(15)N values for Rock Iguanas (Cyclura spp.) to better understand isotopic fractionation and estimate wild reptile foraging ecology. The Δ(13)C and Δ(15)N values between diet and skin, blood, and scat were determined from juvenile and adult iguanas held for 1 year on a known diet. We measured relationships between iguana discrimination factors and size/age and quantified effects of lipid extraction and acid treatment on stable isotope values from iguana tissues. Isotopic and elemental compositions were determined by Dumas combustion using an elemental analyzer coupled to an isotope ratio mass spectrometer using standards of known composition. The Δ(13)C and Δ(15)N values ranged from -2.5 to +6.5‰ and +2.2 to +7.5‰, respectively, with some differences among tissues and between juveniles and adults. The Δ(13)C values from blood and skin differed among species, but not the Δ(15)N values. The Δ(13)C values from blood and skin and Δ(15)N values from blood were positively correlated with size/age. The Δ(13)C values from scat were negatively correlated with size (not age). Treatment with HCl (scat) and lipid extraction (skin) did not affect the isotope values. These results should aid in the understanding of processes driving stable carbon and nitrogen isotope discrimination factors in reptiles. We provide estimates of Δ(13)C and Δ(15)N values and linear relationships between iguana size/age and discrimination factors for the best interpretation of wild reptile foraging ecology. Copyright © 2015 John Wiley & Sons, Ltd.

Preservation Methods Alter Carbon and Nitrogen Stable Isotope Values in Crickets (Orthoptera: Grylloidea)

PubMed Central

Jesus, Fabiene Maria; Pereira, Marcelo Ribeiro; Rosa, Cassiano Sousa; Moreira, Marcelo Zacharias; Sperber, Carlos Frankl

2015-01-01

Stable isotope analysis (SIA) is an important tool for investigation of animal dietary habits for determination of feeding niche. Ideally, fresh samples should be used for isotopic analysis, but logistics frequently demands preservation of organisms for analysis at a later time. The goal of this study was to establish the best methodology for preserving forest litter-dwelling crickets for later SIA analysis without altering results. We collected two cricket species, Phoremia sp. and Mellopsis doucasae, from which we prepared 70 samples per species, divided among seven treatments: (i) freshly processed (control); preserved in fuel ethanol for (ii) 15 and (iii) 60 days; preserved in commercial ethanol for (iv) 15 and (v) 60 days; fresh material frozen for (vi) 15 and (vii) 60 days. After oven drying, samples were analyzed for δ 15N, δ 13C values, N(%), C(%) and C/N atomic values using continuous flow isotope ratio mass spectrometry. All preservation methods tested, significantly impacted δ 13C and δ 15N and C/N atomic values. Chemical preservatives caused δ 13C enrichment as great as 1.5‰, and δ 15N enrichment as great as 0.9‰; the one exception was M. doucasae stored in ethanol for 15 days, which had δ 15N depletion up to 1.8‰. Freezing depleted δ 13C and δ 15N by up to 0.7 and 2.2‰, respectively. C/N atomic values decreased when stored in ethanol, and increased when frozen for 60 days for both cricket species. Our results indicate that all preservation methods tested in this study altered at least one of the tested isotope values when compared to fresh material (controls). We conclude that only freshly processed material provides adequate SIA results for litter-dwelling crickets. PMID:26390400

Preservation Methods Alter Carbon and Nitrogen Stable Isotope Values in Crickets (Orthoptera: Grylloidea).

PubMed

Jesus, Fabiene Maria; Pereira, Marcelo Ribeiro; Rosa, Cassiano Sousa; Moreira, Marcelo Zacharias; Sperber, Carlos Frankl

2015-01-01

Stable isotope analysis (SIA) is an important tool for investigation of animal dietary habits for determination of feeding niche. Ideally, fresh samples should be used for isotopic analysis, but logistics frequently demands preservation of organisms for analysis at a later time. The goal of this study was to establish the best methodology for preserving forest litter-dwelling crickets for later SIA analysis without altering results. We collected two cricket species, Phoremia sp. and Mellopsis doucasae, from which we prepared 70 samples per species, divided among seven treatments: (i) freshly processed (control); preserved in fuel ethanol for (ii) 15 and (iii) 60 days; preserved in commercial ethanol for (iv) 15 and (v) 60 days; fresh material frozen for (vi) 15 and (vii) 60 days. After oven drying, samples were analyzed for δ15N, δ13C values, N(%), C(%) and C/N atomic values using continuous flow isotope ratio mass spectrometry. All preservation methods tested, significantly impacted δ13C and δ15N and C/N atomic values. Chemical preservatives caused δ13C enrichment as great as 1.5‰, and δ15N enrichment as great as 0.9‰; the one exception was M. doucasae stored in ethanol for 15 days, which had δ15N depletion up to 1.8‰. Freezing depleted δ13C and δ15N by up to 0.7 and 2.2‰, respectively. C/N atomic values decreased when stored in ethanol, and increased when frozen for 60 days for both cricket species. Our results indicate that all preservation methods tested in this study altered at least one of the tested isotope values when compared to fresh material (controls). We conclude that only freshly processed material provides adequate SIA results for litter-dwelling crickets.

Spatial and Temporal Variations in Stable Carbon (δ13C) and Nitrogen (δ15N) Isotopic Composition of Symbiotic Scleractinian Corals

PubMed Central

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 (δ13C) and nitrogen (δ15N) 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 13C-depleted and 15N-enriched relative to corals and photosymbionts from less turbid sites. However, differences in both δ13C and δ15N between coral host tissues and their photosymbionts (Δhost-photosymbionts 13C and Δhost-photosymbionts 15N) 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 δ13C and enriched δ15N 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 δ13C and δ15N values of coral host and photosymbiont tissues and in Δhost-photosymbionts 13C and Δhost-photosymbionts 15N 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 heterotrophy with higher food availability thus appears to be species-specific. PMID:24312542

Impacts of sea cucumber farming on biogeochemical characteristics in the Yellow River estuary, Northern China

NASA Astrophysics Data System (ADS)

Fu, Jing; Yokoyama, Hisashi; Cui, Baoshan; Zhou, Jin; Yan, Jiaguo; Ma, Xu; Shibata, Shozo

2017-02-01

To investigate the potential environmental effects of pond farming for Apostichopus japonicas in Yellow River estuary, we examined discrepancies of distance-based typical pollution indicators (TOC, TN, NO3-, NH4+, NO2- and PO43-) and biochemical tracers (δ13C and δ15N) in water column and sediment, as well as dietary characteristics of dominant macrobenthos between farming and non-farming areas. The results revealed that studied variables in water column showed no uniform spatial differences. Meanwhile, those in sediment displayed similar decrease tendencies from farming pond to the adjacent tidal flat, which was considered to represent the environmental effects of farming. Biochemical tracers (δ13C and δ15N) in both water column and sediment confirmed the origin of organic matters from the aquaculture waste. The detectable dispersion distance of aquaculture waste was restricted to an area within 50 m distance as determined by most variables in sediment (TOC, TN, NO3- and NH4+), particularly by C:N ratio and δ13C with which origins of the wastes were traced. Bayesian mixing models indicated that in the farming area BMA had a larger contribution, while POM(marine) showed a smaller contribution to the diets of Helice tridens and Macrophthalmus abbreviates compared to those in the non-farming area. The overall results showed that pond farming for Apostichopus japonicus in the Yellow River estuary altered the local environment to a certain extent. For methodological consideration, sediment biogeochemical characteristics as a historical recorder much more effectively reflected aquaculture waste accumulation, and stable isotope approaches are efficient in tracing the origin and extent of various allogenous sources.

A Dual-Carbon-and-Nitrogen Stable Isotope Ratio Model Is Not Superior to a Single-Carbon Stable Isotope Ratio Model for Predicting Added Sugar Intake in Southwest Virginian Adults12

PubMed Central

Hedrick, Valisa E; Zoellner, Jamie M; Jahren, A Hope; Woodford, Natalie A; Bostic, Joshua N; Davy, Brenda M

2015-01-01

Background: An objective measure of added sugar (AS) and sugar-sweetened beverage (SSB) intake is needed. The δ13C value of finger-stick blood is a novel validated biomarker of AS/SSB intake; however, nonsweetener corn products and animal protein also carry a δ13C value similar to AS sources, which may affect blood δ13C values. The δ15N value of blood has been proposed as a “correction factor” for animal protein intake. Objectives: The objectives were to 1) identify foods associated with δ13C and δ15N blood values, 2) determine the contribution of nonsweetener corn to the diet relative to AS intake, and 3) determine if the dual-isotope model (δ13C and δ15N) is a better predictor of AS/SSB intake than δ13C alone. Methods: A cross-sectional sample of southwest Virginian adults (n = 257; aged 42 ± 15 y; 74% overweight/obese) underwent dietary intake assessments and provided finger-stick blood samples, which were analyzed for δ13C and δ15N values by using natural abundance stable isotope mass spectrometry. Statistical analyses included ANOVAs, paired-samples t tests, and multiple linear regressions. Results: The mean ± SD daily AS intake was 88 ± 59 g and nonsweetener corn intake was 13 ± 13 g. The mean δ13C value was −19.1 ± 0.9‰, which was significantly correlated with AS and SSB intakes (r = 0.32 and 0.39, respectively; P ≤ 0.01). The δ13C value and nonsweetener corn intake and the δ15N value and animal protein intake were not correlated. AS intake was significantly greater than nonsweetener corn intake (mean difference = 76.2 ± 57.2 g; P ≤ 0.001). The δ13C value was predictive of AS/SSB intake (β range: 0.28–0.35; P ≤ 0.01); however, δ15N was not predictive and minimal increases in R2 values were observed when the δ15N value was added to the model. Conclusions: The data do not provide evidence that the dual-isotope method is superior for predicting AS/SSB intakes within a southwest Virginian population. Our results support the potential of the δ13C value of finger-stick blood to serve as an objective measure of AS/SSB intake. This trial was registered at clinicaltrials.gov as NCT02193009. PMID:25855120

Characterization of organic matter in lake sediments from Minnesota and Yellowstone National Park

USGS Publications Warehouse

Dean, Walter E.

2006-01-01

Samples of sediment from lakes in Minnesota and Yellowstone National Park (YNP) were analyzed for organic carbon (OC), hydrogen richness by Rock-Eval pyrolysis, and stable carbon- and nitrogen-isotope composition of bulk organic matter. Values of delta 13C of lake plankton tend to be around -28 to -32 parts per thousand (0/00). Organic matter with values of delta 13C in the high negative 20s overlap with those of organic matter derived from C3 higher terrestrial plants but are at least 10 0/00 more depleted in 13C than organic matter derived from C4 terrestrial plants. If the organic matter is produced mainly by photosynthetic plankton and is not oxidized in the water column, there may be a negative correlation between H-richness (Rock-Eval pyrolysis H-index) and delta 13C, with more H-rich, algal organic matter having lower values of delta 13C. However, if aquatic organic matter is oxidized in the water column, or if the organic matter is a mixture of terrestrial and aquatic organic matter, then there may be no correlation between H-richness and carbon-isotopic composition. Values of delta 13C lower than about -28 0/00 probably indicate a contribution of bacterial biomass produced in the hypolimnion by chemoautotrophy or methanotrophy. In highly eutrophic lakes in which large amounts of 13C-depleted organic matter is continually removed from the epilimnion by photosynthesis throughout the growing season, the entire carbon reservoir in the epilimnion may become severely 13C-enriched so that 13C-enriched photosynthetic organic matter may overprint 13C-depleted chemosynthetic bacterial organic matter produced in the hypolimnon. Most processes involved with the nitrogen cycle in lakes, such as production of ammonia and nitrate, tend to produce 15N-enriched values of delta 15N. Most Minnesota lake sediments are 15N-enriched. However, some of the more OC-rich sediments have delta 15N values close to zero (delta 15N of air), suggesting that organic matter production is by nitrogen fixation, which further implies that nitrogen is limiting. Most lakes from YNP also have values of delta 15N near zero.

Grissom AFB, Indiana. Revised Uniform Summary of Surface Weather Observations (RUSSWO). Parts A-F.

DTIC Science & Technology

1983-07-01

8.8i 15.51 1b.3 27.1 7%39 USAFETAC 0 TOS N. OL. ), O~ Poyaw 0mo IMS rOR Omm V~ Jm- - - - - -- - - -- - - - - - - U A 2AL CLIMATOLOY B’ANCH 2 Z .Ac...2Z812.o3410.911 S. 945 ,.137 6.561 6.607 8.977 9.95612.15813.1I5 19.923 6~ 3 .46 927. 920 --U 9 R. Z 9Z5. 3 U. 9CC 93 Q 900 927. 1 C9 4. 13. 11.7 3j

Interindividual differences in embodied marginalization: Osteological and stable isotope analyses of antebellum enslaved individuals.

PubMed

Dent, Sophia C

2017-07-08

Through pathological and stable isotope analyses, this study probes the stressors, disease ecology, and diets of enslaved individuals from an antebellum plantation cemetery. The study aims to highlight how interindividual isotopic differences reveal that marginalization is not uniformly experienced or embodied. The cemetery population consists of 16 individuals; dental and skeletal pathological indicators were collected for all individuals, and light stable isotope ratios (δ 15 N, δ 13 C) were generated from the collagen and hydroxyapatite of nine individuals. The analyzed individuals have high frequencies of enamel defects-similar to contemporaneous enslaved cemetery individuals-and particularly high frequencies of carious lesions. Skeletal analysis shows evidence of chronic conditions among several individuals, two of whom likely have tuberculosis. Although the sample size is small, stable isotope values display interesting trends: there is interindividual heterogeneity in δ 13 C values, and most subadults from the cemetery have lower δ 15 N and higher δ 13 C values than the sampled adults. These relationships can be tested with larger datasets and have the potential to reveal important information about slave foodways and the broader experience of enslavement. The results of this study suggest that racial discrimination, enslavement, and age do not fully account for the heterogeneity in degree of embodied stressors. There are likely other factors at play, intersecting with the aforementioned, that influenced the lived experience of slavery and the degree of marginalization. © 2017 Wiley Periodicals, Inc.

Structure of indazole N1-oxide derivatives studied by X-ray, theoretical methods, 1H, 13C, 15N NMR and EI/MS

NASA Astrophysics Data System (ADS)

Gerpe, Alejandra; Piro, Oscar E.; Cerecetto, Hugo; González, Mercedes

2007-12-01

A series of indazole N1-oxide derivatives has been spectroscopically studied in solution using 1H, 13C, and 15N NMR based on pulsed field gradient selected PFG 1H sbnd X (X = 13C and 15N) gHMQC and gHMBC experiments. Some indazoles were prepared using a new methodology to compare its spectral and structural data with the indazole N1-oxide parent compounds. The 13C resonances of the indazole N1-oxide carbon 3 and 7a demonstrate the N-oxide push-electron capability. The 15N resonances of the indazole N-oxide, nitrogen 1, are near to 30 ppm more shielded than the corresponding values in the indazole heterocycle (deoxygenated form). Moreover, the structures of one indazole and one indazole N-oxide were unambiguously confirmed by X-ray crystallography. The solid state structures were contrasted with the theoretical ones obtained in vacuo at different calculus level. The aromaticity of the derivatives was studied analyzing the H sbnd H coupling constants of indazole's aromatic hydrogens and measuring C sbnd C distances in the solid state. The fragmentation that takes place in EI/MS was gathered for all the indazole N-oxide derivatives and the general fragmentation pattern analyzed.

Carbon and nitrogen isotope systematics in diamond: Different sensitivities to isotopic fractionation or a decoupled origin?

NASA Astrophysics Data System (ADS)

Hogberg, K.; Stachel, T.; Stern, R. A.

2016-11-01

Using stable isotope data obtained on multiple aliquots of diamonds from worldwide sources, it has been argued that carbon and nitrogen in diamond are decoupled. Here we re-investigate the carbon-nitrogen relationship based on the most comprehensive microbeam data set to date of stable isotopes and nitrogen concentrations in diamonds (n = 94) from a single locality. Our diamond samples, derived from two kimberlites in the Chidliak Field (NE Canada), show large variability in δ13C (- 28.4 ‰ to - 1.1‰, mode at - 5.8‰), δ15N (- 5.8 to + 18.8‰, mode at - 3.0‰) and nitrogen contents ([N]; 3800 to less than 1 at.ppm). In combination, cathodoluminescence imaging and microbeam analyses reveal that the diamonds grew from multiple fluid pulses, with at least one major hiatus documented in some samples that was associated with a resorption event and an abrupt change from low δ13C and [N] to mantle-like δ13C and high [N]. Overall, δ13C appears to be uncorrelated to δ15N and [N] on both the inter- and intra-diamond levels. Co-variations of δ15N-log[N], however, result in at least two parallel, negatively correlated linear arrays, which are also present on the level of the individual diamonds falling on these two trends. These arrays emerge from the two principal data clusters, are characterized by slightly negative and slightly positive δ15N (about - 3 and + 2‰, respectively) and variable but overall high [N]. Using published values for the diamond-fluid nitrogen isotope fractionation factor and nitrogen partition coefficient, these trends are perfectly reproduced by a Rayleigh fractionation model. Overall, three key elements are identified in the formation of the diamond suite studied: (1.) a low δ13C and low [N] component that possibly is directly associated with an eclogitic diamond substrate or introduced during an early stage fluid event. (2.) Repeated influx of a variably nitrogen-rich mantle fluid (mildly negative δ13C and δ15N). (3.) In waning stages of influx, availability of the mantle-type fluid at the site of diamond growth became limited, leading to Rayleigh fractionation. These fractionation trends are clearly depicted by δ15N-[N] but are not detected when examining co-variation diagrams involving δ13C. Also on the level of individual diamonds, large (≥ 5‰) variations in δ15N are associated with δ13C values that typically are constant within analytical uncertainty. The much smaller isotope fractionation factor for carbon (considering carbonate- or methane-rich fluids as possible carbon sources) compared to nitrogen leads to an approximately one order of magnitude lower sensitivity of δ13C values to Rayleigh fractionation processes (i.e. during fractionation, a 1‰ change in δ13C is associated with a 10‰ change in δ15N). As a consequence, even minor heterogeneity in the primary isotopic composition of diamond forming carbon (e.g., due to addition of minor subducted carbon) will completely blur any possible co-variations with δ15N or [N]. We suggest this strong difference in isotope effects for C and N to be the likely cause of observations of an apparently decoupled behaviour of carbon and nitrogen isotopes in diamond.

ALMA OBSERVATIONS OF HCN AND ITS ISOTOPOLOGUES ON TITAN

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

Molter, Edward M.; Nixon, C. A.; Cordiner, M. A.

2016-08-01

We present sub-millimeter spectra of HCN isotopologues on Titan, derived from publicly available ALMA flux calibration observations of Titan taken in early 2014. We report the detection of a new HCN isotopologue on Titan, H{sup 13}C{sup 15}N, and confirm an earlier report of detection of DCN. We model high signal-to-noise observations of HCN, H{sup 13}CN, HC{sup 15}N, DCN, and H{sup 13}C{sup 15}N to derive abundances and infer the following isotopic ratios: {sup 12}C/{sup 13}C = 89.8 ± 2.8, {sup 14}N/{sup 15}N = 72.3 ± 2.2, D/H = (2.5 ± 0.2) × 10{sup −4}, and HCN/H{sup 13}C{sup 15}N = 5800 ± 270 (1 σ errors). The carbon and nitrogen ratios are consistent with and improve on themore » precision of previous results, confirming a factor of ∼2.3 elevation in {sup 14}N/{sup 15}N in HCN compared to N{sub 2} and a lack of fractionation in {sup 12}C/{sup 13}C from the protosolar value. This is the first published measurement of D/H in a nitrile species on Titan, and we find evidence for a factor of ∼2 deuterium enrichment in hydrogen cyanide compared to methane. The isotopic ratios we derive may be used as constraints for future models to better understand the fractionation processes occurring in Titan’s atmosphere.« less

(13)C-(15)N correlation via unsymmetrical indirect covariance NMR: application to vinblastine.

PubMed

Martin, Gary E; Hilton, Bruce D; Blinov, Kirill A; Williams, Antony J

2007-12-01

Unsymmetrical indirect covariance processing methods allow the derivation of hyphenated 2D NMR data from the component 2D spectra, potentially circumventing the acquisition of the much lower sensitivity hyphenated 2D NMR experimental data. Calculation of HSQC-COSY and HSQC-NOESY spectra from GHSQC, COSY, and NOESY spectra, respectively, has been reported. The use of unsymmetrical indirect covariance processing has also been applied to the combination of (1)H- (13)C GHSQC and (1)H- (15)N long-range correlation data (GHMBC, IMPEACH, or CIGAR-HMBC). The application of unsymmetrical indirect covariance processing to spectra of vinblastine is now reported, specifically the algorithmic extraction of (13)C- (15)N correlations via the unsymmetrical indirect covariance processing of the combination of (1)H- (13)C GHSQC and long-range (1)H- (15)N GHMBC to produce the equivalent of a (13)C- (15)N HSQC-HMBC correlation spectrum. The elimination of artifact responses with aromatic solvent-induced shifts (ASIS) is shown in addition to a method of forecasting potential artifact responses through the indirect covariance processing of the GHSQC spectrum used in the unsymmetrical indirect covariance processing.

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

PubMed

Stueber, Dirk; Grant, David M

2002-09-04

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

Asymmetric synthesis of [2,3-(13)C(2),(15)N]-4-benzyloxy-5,6-diphenyl-2,3,5,6-tetrahydro-4H-oxazine-2-one via lipase TL-mediated kinetic resolution of benzoin: general procedure for the synthesis of [2,3-(13)C(2),(15)N]-L-alanine.

PubMed

Aoyagi, Y; Iijima, A; Williams, R M

2001-11-30

Lipase TL-mediated kinetic resolution of benzoin proceeded to give the corresponding optically pure (R)-benzoin (R)-1. On the other hand, (S)-benzoin O-acetate (S)-7 could be hydrolyzed without epimerization to give (S)-benzoin (S)-1 under alkaline conditions. Furthermore, both enantiomers of benzoin (1) were converted to [(15)N]-(1R,2S)- and (1S,2R)- 2-amino-1,2-diphenylethanol (3a and 3b), respectively, according to the procedure reported previously. [2,3-(13)C(2),(15)N]-(5S,6R)-4-benzyloxy-5,6-diphenyl-2,3,5,6-tetrahydro-4H-oxazine-2-one (10) was synthesized from ethyl [1,2-(13)C(2)]bromoacetate and (1R,2S)-2-amino-1,2-diphenylethanol (3b) in three steps. Finally, [2,3-(13)C(2),(15)N]-L-alanine (12) was prepared via alkylation of the lactone 10 and hydrogenation of the alkylated product 11.

Using stable isotopes of albacore tuna and predictive models to characterize bioregions and examine ecological change in the SW Pacific Ocean

NASA Astrophysics Data System (ADS)

Pethybridge, Heidi R.; Young, Jock W.; Kuhnert, Petra M.; Farley, Jessica H.

2015-05-01

Broad-scale food web inferences of 534 albacore tuna, Thunnus alalunga, in the south-west Pacific Ocean in 2009 and 2010 were made using bulk nitrogen (δ15N) and carbon (δ13C) stable isotopes. Condition was also examined for the same fish using C:N ratios. A Generalized Additive Modeling (GAM) approach was used to analyze spatio-temporal, biological and environmental drivers that impact the distribution of tuna isotopes and to create oceanographic maps. Based on model formulations, five bioregions with distinct isotopic signatures were identified and were related to known biological, nutrient cycling and oceanographic (temperature, primary productivity and eddy) features associated with the East Australian Current. δ15N values showed a large-scale, uniform latitudinal gradient decreasing from the south to north, in a region encompassing oligotrophic waters in the Coral Sea. In contrast, δ13C values were lower in the nutrient rich Tasman Sea waters and offshore East Australia. C:N ratios suggested that albacore occupying southern and offshore waters were in better condition. Ontogenetic trends in all three biochemical parameters were identified and related to differences in size distribution. Regional-specific temporal variations were detected including similar monthly changes for both isotopes and significantly less enriched δ13C (by 1.9‰) than in previous work undertaken in 2006, potentially signifying a substantial shift in the carbon cycle that supports food webs off central east Australia. Our results showed that isotopic measurements in tuna and the GAM framework provide powerful tools to assess ecosystem functioning and change by linking sources of nutrients and organic matter to local food web assembly. Such knowledge is vital to support an ecosystem based approach to fisheries management including biogeochemical whole-of-ecosystem models and monitoring programs at regional and landscape-scales.

Carbon and nitrogen isotopic compositions of alkyl porphyrins from the Triassic Serpiano oil shale

NASA Technical Reports Server (NTRS)

Chicarelli, M. I.; Hayes, J. M.; Popp, B. N.; Eckardt, C. B.; Maxwell, J. R.

1993-01-01

The carbon and nitrogen isotopic compositions of seven of the most abundant alkylporphyrins from the Serpiano oil shale (marine, Triassic) were determined. For the C31 and C32 butanoporphyrins, values of delta 13CPDB and delta 15NAIR averaged -24.0% and -3.1%. In contrast, the C31 and C32 methylpropanoporphyrins, DPEP, and a C30 13-nor etioporphyrin had delta 13C and delta 15N values averaging -27.5 and -3.3%, respectively. Carbon and nitrogen isotopic values for kerogen averaged -30.8 and -0.9, whereas those for total extract averaged -31.6, and -4.0%. The butanoporphyrins apparently derive from a biological source different from that giving rise to the other porphyrins, their 13C enrichment not being related to carbon isotopic fractionation accompanying diagenetic reactions. The delta 15N values for all the porphyrins indicate that the depletion of 15N observed in the kerogen is of primary origin. Consistent with the very high abundance of hopanoids and methyl hopanoids in the aliphatic hydrocarbon fraction, it is suggested that cyanobacterial fixation of N2 may have been the main cause of 15N depletion.

Water-Solubilized, Cap-Stabilized, Helical Polyalanines: Calibration Standards for NMR and CD Analyses

PubMed Central

Heitmann, Björn; Job, Gabriel E.; Kennedy, Robert J.; Walker, Sharon M.; Kemp, Daniel S.

2006-01-01

NMR and CD studies are reported for two length series of solubilized, spaced, highly helical polyalanines that are N-capped by the optimal helix stabilizer βAsp-Hel and C-capped by β-aminoalanine beta and that are studied in water at 2 °C, pH 1–8. NMR analysis yields a structural characterization of the peptide AcβAspHelAla8betaNH2 and selected members of one βAspHelAlanbeta series. At pH > 4.5 the βAspHel cap provides a preorganized triad of carboxylate anion and two amide residues that is complementary to the helical polyalanine N-terminus. The C-terminal β-aminoalanine assumes a helix-stabilizing conformation consistent with literature precedents. H(N)CO NMR experiments applied to capped, uniformly 13C- and 15N-labeled Ala8 and Ala12 peptides define Alan hydrogen bonding signatures as α-helical without detectable 310 character. Relative NH→ND exchange rates yield site protection factors PFi that define uniquely high fractional helicities FH for the peptide Alan regions. These Alan calibration series, studied in water and lacking helix-stabilizing tertiary structure, yield the first 13C NMR chemical shifts, 3JHNHα coupling constants, and CD ellipticities [θMolar]λ,n characteristic of a fully helical alanine within an Alan context. CD data are used to assign parameters X and [θ]λ,∞, required for rigorous calculation of FH values from CD ellipticities. PMID:15701003

Application of isotopic techniques to investigate the impact of insect herbivory on C and N cycling in a grassland system - a mesocosm study

NASA Astrophysics Data System (ADS)

Potthast, Karin; Meyer, Stefanie; Gleixner, Gerd; Crecelius, Anna; Schubert, Ulrich; Michalzik, Beate

2017-04-01

Ecosystem disturbances like insect pests induce time and space limited process heterogeneity that allow to quantify changes in biogeochemical reaction rates. Insect pests are known to impact element and organic matter (OM) cycling in ecosystems by defoliation and deposition of fecal material. To study the effects of such trophic interactions on OM and nutrient cycling in a grassland system under herbivore attack, a laboratory mesocosm experiment with grass (Dactylis glomerata) and grasshoppers (Chorthippus dorsatus) was conducted. In 12 mesocosms (50 cm in diameter, 100 cm in height) D. glomerata was sown in pasture topsoil (0-12 cm of a Calcaric Cambisol (Siltic), Hainich region, Germany) and left to grow for one year under constant climatic conditions (15°C) to establish a well-developed root system. In 2015, the mesocosm was labeled over 5 days using 13CO2-gas and 15N labeled feces (δ15N: 58‰) in order to trace the fate of C and N in above- and belowground plant organs (root, leave), insects, feces, soil, and soil solution. In three replicates, the following treatments were conducted: control, 13CO2-labelling, 13CO2-labelling+20 grasshoppers, and 13CO2-labelling+20 grasshoppers +15N-labeled feces (+9.2 µg N*cm-2). During incubation, the mesocosms were irrigated (13 mm) and throughfall and soil solutions were sampled. After incubation, solutions, cold water extracts as well as microbial biomass (chloroform-fumigation) of two soil depths (0-4, 4-12 cm) were analyzed for DOC, δ13DOC, and dissolved N. Furthermore, TOC, δ13C, TN and δ15N values of all collected compartments were determined. In general, 13CO2-pulse labelling showed that after 5 days of incubation not only grasshopper feces but also leachates of feces were significantly enriched in 13C. Based on δ13C-values, herbivory induced a stronger 13C-enrichment in roots while shoots were less enriched. The input of 13DOC indicates a fast cycling of leaf-C via grasshopper and feces to the soil solution, soil microbes and grass roots. This was further confirmed by a 80 % mass loss and by a reduced N amount (-91%) of labeled feces. This may indicate a rapid release of N via leaching, and root-uptake (-0.82±0.28‰) compared to treatments without 15N (-1.54±0.12‰). 15N in grass leaves was not found to be enriched, however, significantly higher δ15N values were found in freshly excreted feces (0.62±0.4‰) compared to those of mesocosms without 15N addition (-0.14 ±0.27‰). Hence, we hypothesize that part of the labeled N was also rapidly assimilated within plant and microbial biomass, taken up by grasshoppers, and returned via feces. The N amount in soil solution and cold water extracts did not increase due to herbivory supporting the assumption of a rapid plant uptake of released N. The low N concentrations of the mineral soil (0.14 %) and in soil solutions (1-2.3 mg L-1) point to very low N availability for the grass. We conclude that on the short-time scale in N-limited pasture systems heavy insect herbivory would not result in significant N leaching from the ecosystem.

δ13C and δ15N Values of Sediment-trap Particles in the Japan and Yamato Basins and Comparison with the Core-top Values in the East/Japan Sea

NASA Astrophysics Data System (ADS)

Khim, Boo-Keun; Otosaka, Shigeyoshi; Park, Kyung-Ae; Noriki, Shinichiro

2018-03-01

Investigation of sediment-trap deployments in the East/Japan Sea (EJS) showed that distinct seasonal variations in particulate organic carbon (POC) fluxes of intermediate-water sediment-traps clearly corresponded to changes in chlorophyll a concentrations estimated from SeaWiFS data. The prominent high POC flux periods (e.g., March) were strongly correlated with the enhanced surface-water phytoplankton blooms. Deep-water sedimenttraps exhibited similar variation patterns to intermediate-water sediment-traps. However, their total flux and POC flux were higher than those of intermediate-water sediment-traps during some months (e.g., April and May), indicating the lateral delivery of some particles to the deep-water sediment-traps. Distinct seasonal δ13C and δ15N variations in settling particles of the intermediate-water sediment-traps were observed, strongly supporting the notion of seasonal primary production. Seasonal variations in δ13C and δ15N values from the deep-water sediment-traps were similar to those of the intermediate-water sediment-traps. However, the difference in δ13C and δ15N values between the intermediate-water and the deepwater sediment-traps may be attributed to degradation of organic matter as it sank through the water column. Comparison of fluxweighted δ13C and δ15N mean values between the deep-water sediment-traps and the core-top sediments showed that strong selective loss of organic matter components (lipids) depleted in 13C and 15N occurred during sediment burial. Nonetheless, the results of our study indicate that particles in the deep-water sediment-trap deposited as surface sediments on the seafloor preserve the record of surface-water conditions, highlighting the usefulness of sedimentary δ13C and δ15N values as a paleoceanographic application in the EJS.

Reduced dimensionality tailored HN(C)N experiments for facile backbone resonance assignment of proteins through unambiguous identification of sequential HSQC peaks

NASA Astrophysics Data System (ADS)

Kumar, Dinesh

2013-12-01

Two novel reduced dimensionality (RD) tailored HN(C)N [S.C. Panchal, N.S. Bhavesh, R.V. Hosur, Improved 3D triple resonance experiments, HNN and HN(C)N, for HN and 15N sequential correlations in (13C, 15N) labeled proteins: application to unfolded proteins, J. Biomol. NMR 20 (2001) 135-147] experiments are proposed to facilitate the backbone resonance assignment of proteins both in terms of its accuracy and speed. These experiments - referred here as (4,3)D-hNCOcaNH and (4,3)D-hNcoCANH - exploit the linear combination of backbone 15N and 13C‧/13Cα chemical shifts simultaneously to achieve higher peak dispersion and randomness along their respective F1 dimensions. Simply, this has been achieved by modulating the backbone 15N(i) chemical shifts with that of 13C‧ (i - 1)/13Cα (i - 1) spins following the established reduced dimensionality NMR approach [T. Szyperski, D.C. Yeh, D.K. Sukumaran, H.N. Moseley, G.T. Montelione, Reduced-dimensionality NMR spectroscopy for high-throughput protein resonance assignment, Proc. Natl. Acad. Sci. USA 99 (2002) 8009-8014]. Though the modification is simple it has resulted an ingenious improvement of HN(C)N both in terms of peak dispersion and easiness of establishing the sequential connectivities. The increased dispersion along F1 dimension solves two purposes here: (i) resolves the ambiguities arising because of degenerate 15N chemical shifts and (ii) reduces the signal overlap in F2(15N)-F3(1H) planes (an important requisite in HN(C)N based assignment protocol for facile and unambiguous identification of sequentially connected HSQC peaks). The performance of both these experiments and the assignment protocol has been demonstrated using bovine apo Calbindin-d9k (75 aa) and urea denatured UNC60B (a 152 amino acid ADF/cofilin family protein of Caenorhabditis elegans), as representatives of folded and unfolded protein systems, respectively.

A new organic reference material, L-glutamic acid, USGS41a, for δ13C and δ15N measurements − a replacement for USGS41

USGS Publications Warehouse

Qi, Haiping; Coplen, Tyler B.; Mroczkowski, Stanley J.; Brand, Willi A.; Brandes, Lauren; Geilmann, Heike; Schimmelmann, Arndt

2016-01-01

RationaleThe widely used l-glutamic acid isotopic reference material USGS41, enriched in both 13C and 15N, is nearly exhausted. A new material, USGS41a, has been prepared as a replacement for USGS41.MethodsUSGS41a was prepared by dissolving analytical grade l-glutamic acid enriched in 13C and 15N together with l-glutamic acid of normal isotopic composition. The δ13C and δ15N values of USGS41a were directly or indirectly normalized with the international reference materials NBS 19 calcium carbonate (δ13CVPDB = +1.95 mUr, where milliurey = 0.001 = 1 ‰), LSVEC lithium carbonate (δ13CVPDB = −46.6 mUr), and IAEA-N-1 ammonium sulfate (δ15NAir = +0.43 mUr) and USGS32 potassium nitrate (δ15N = +180 mUr exactly) by on-line combustion, continuous-flow isotope-ratio mass spectrometry, and off-line dual-inlet isotope-ratio mass spectrometry.ResultsUSGS41a is isotopically homogeneous; the reproducibility of δ13C and δ15N is better than 0.07 mUr and 0.09 mUr, respectively, in 200-μg amounts. It has a δ13C value of +36.55 mUr relative to VPDB and a δ15N value of +47.55 mUr relative to N2 in air. USGS41 was found to be hydroscopic, probably due to the presence of pyroglutamic acid. Experimental results indicate that the chemical purity of USGS41a is substantially better than that of USGS41.ConclusionsThe new isotopic reference material USGS41a can be used with USGS40 (having a δ13CVPDB value of −26.39 mUr and a δ15NAir value of −4.52 mUr) for (i) analyzing local laboratory isotopic reference materials, and (ii) quantifying drift with time, mass-dependent isotopic fractionation, and isotope-ratio-scale contraction for isotopic analysis of biological and organic materials. Published in 2016. This article is a U.S. Government work and is in the public domain in the USA.

A new organic reference material, l-glutamic acid, USGS41a, for δ(13) C and δ(15) N measurements - a replacement for USGS41.

PubMed

Qi, Haiping; Coplen, Tyler B; Mroczkowski, Stanley J; Brand, Willi A; Brandes, Lauren; Geilmann, Heike; Schimmelmann, Arndt

2016-04-15

The widely used l-glutamic acid isotopic reference material USGS41, enriched in both (13) C and (15) N, is nearly exhausted. A new material, USGS41a, has been prepared as a replacement for USGS41. USGS41a was prepared by dissolving analytical grade l-glutamic acid enriched in (13) C and (15) N together with l-glutamic acid of normal isotopic composition. The δ(13) C and δ(15) N values of USGS41a were directly or indirectly normalized with the international reference materials NBS 19 calcium carbonate (δ(13) CVPDB = +1.95 mUr, where milliurey = 0.001 = 1 ‰), LSVEC lithium carbonate (δ(13) CVPDB = -46.6 mUr), and IAEA-N-1 ammonium sulfate (δ(15) NAir = +0.43 mUr) and USGS32 potassium nitrate (δ(15) N = +180 mUr exactly) by on-line combustion, continuous-flow isotope-ratio mass spectrometry, and off-line dual-inlet isotope-ratio mass spectrometry. USGS41a is isotopically homogeneous; the reproducibility of δ(13) C and δ(15) N is better than 0.07 mUr and 0.09 mUr, respectively, in 200-μg amounts. It has a δ(13) C value of +36.55 mUr relative to VPDB and a δ(15) N value of +47.55 mUr relative to N2 in air. USGS41 was found to be hydroscopic, probably due to the presence of pyroglutamic acid. Experimental results indicate that the chemical purity of USGS41a is substantially better than that of USGS41. The new isotopic reference material USGS41a can be used with USGS40 (having a δ(13) CVPDB value of -26.39 mUr and a δ(15) NAir value of -4.52 mUr) for (i) analyzing local laboratory isotopic reference materials, and (ii) quantifying drift with time, mass-dependent isotopic fractionation, and isotope-ratio-scale contraction for isotopic analysis of biological and organic materials. Published in 2016. This article is a U.S. Government work and is in the public domain in the USA. Published in 2016. This article is a U.S. Government work and is in the public domain in the USA.

Oligomeric complexes of some heteroaromatic ligands and aromatic diamines with rhodium and molybdenum tetracarboxylates: 13C and 15N CPMAS NMR and density functional theory studies.

PubMed

Leniak, Arkadiusz; Kamieński, Bohdan; Jaźwiński, Jarosław

2015-05-01

Seven new oligomeric complexes of 4,4'-bipyridine; 3,3'-bipyridine; benzene-1,4-diamine; benzene-1,3-diamine; benzene-1,2-diamine; and benzidine with rhodium tetraacetate, as well as 4,4'-bipyridine with molybdenum tetraacetate, have been obtained and investigated by elemental analysis and solid-state nuclear magnetic resonance spectroscopy, (13)C and (15)N CPMAS NMR. The known complexes of pyrazine with rhodium tetrabenzoate, benzoquinone with rhodium tetrapivalate, 4,4'-bipyridine with molybdenum tetrakistrifluoroacetate and the 1 : 1 complex of 2,2'-bipyridine with rhodium tetraacetate exhibiting axial-equatorial ligation mode have been obtained as well for comparison purposes. Elemental analysis revealed 1 : 1 complex stoichiometry of all complexes. The (15)N CPMAS NMR spectra of all new complexes consist of one narrow signal, indicating regular uniform structures. Benzidine forms a heterogeneous material, probably containing linear oligomers and products of further reactions. The complexes were characterized by the parameter complexation shift Δδ (Δδ = δcomplex  - δligand). This parameter ranged from around -40 to -90 ppm in the case of heteroaromatic ligands, from around -12 to -22 ppm for diamines and from -16 to -31 ppm for the complexes of molybdenum tetracarboxylates with 4,4'-bipyridine. The experimental results have been supported by a density functional theory computation of (15)N NMR chemical shifts and complexation shifts at the non-relativistic Becke, three-parameter, Perdew-Wang 91/[6-311++G(2d,p), Stuttgart] and GGA-PBE/QZ4P levels of theory and at the relativistic scalar and spin-orbit zeroth order regular approximation/GGA-PBE/QZ4P level of theory. Nucleus-independent chemical shifts have been calculated for the selected compounds. Copyright © 2015 John Wiley & Sons, Ltd.

Isotopic composition of carbon and nitrogen of suprabenthic fauna in the NW Balearic Islands (western Mediterranean)

NASA Astrophysics Data System (ADS)

Madurell, T.; Fanelli, E.; Cartes, J. E.

Stable isotope (δ 13C and δ 15N) analyses were performed on suprabenthic fauna collected in the western Mediterranean (NW Balearic Islands), at depths ranging between 350 and 780 m. Samples were collected seasonally at bi-monthly intervals during six cruises performed between August 2003 and June 2004, using a Macer-GIROQ suprabenthic sledge (0.5 mm mesh size). Twenty-four separate species (5 mysids, 12 amphipods, 2 cumaceans, 2 isopods, 1 euphausiid, 1 decapod and 1 fish) and bulk copepods were analyzed on a seasonal basis for stable carbon and nitrogen isotopes. Stable nitrogen isotope ratios (δ 15N) ranged from 2.3‰ (the amphipod Lepechinella manco in September 2003) to 13.0‰ (the amphipod Rhachotropis caeca in August 2003). δ 13C values ranged from - 24.2 (the cumacean Campylaspis sulcata in June 2004) to - 16.1 (the amphipod Bruzelia typica in November 2006). Both δ 13C and δ 15N values suggest that there are three trophic levels within the suprabenthic community. However, considering the bathymetric range of the species, the results suggest that the deepest assemblage supported only two trophic levels. The stable isotope ratios of suprabenthic fauna displayed a continuum of values and confirmed a wide spectrum of feeding types (from filter-feeders to predators). In general, and in spite of the poor knowledge about diets available for most suprabenthic species, higher δ 15N were found for carnivorous amphipods (e.g. Rhachotropis spp., Nicippe tumida) consuming copepods. Low overlap for δ 13C and δ 15N values was observed, though δ 15N values where less variable than δ 13C, which suggests high resource partitioning in this assemblage. Seasonal variations in isotopic composition for both δ 13C and δ 15N were low (less than 1‰ and 3‰, respectively) and variable depending on species. Low correlations between δ 13C and δ 15N of suprabenthic fauna were found for all periods studied, though increasing from February 2004 to June 2004 (after the main peak of primary production in surface). C:N ratio (indicator of lipid content) showed higher values in summer than in winter. This suggests that lipid content may explain the seasonal patterns of δ 13C variability and, due to the increase of storage products in phytoplankton and zooplankton, it possibly indicates the peak of primary production at the surface.

Nitrogen and carbon isotopic dynamics of subarctic soils and plants in southern Yukon Territory and its implications for paleoecological and paleodietary studies.

PubMed

Tahmasebi, Farnoush; Longstaffe, Fred J; Zazula, Grant; Bennett, Bruce

2017-01-01

We examine here the carbon and nitrogen isotopic compositions of bulk soils (8 topsoil and 7 subsoils, including two soil profiles) and five different plant parts of 79 C3 plants from two main functional groups: herbs and shrubs/subshrubs, from 18 different locations in grasslands of southern Yukon Territory, Canada (eastern shoreline of Kluane Lake and Whitehorse area). The Kluane Lake region in particular has been identified previously as an analogue for Late Pleistocene eastern Beringia. All topsoils have higher average total nitrogen δ15N and organic carbon δ13C than plants from the same sites with a positive shift occurring with depth in two soil profiles analyzed. All plants analyzed have an average whole plant δ13C of -27.5 ± 1.2 ‰ and foliar δ13C of -28.0 ± 1.3 ‰, and average whole plant δ15N of -0.3 ± 2.2 ‰ and foliar δ15N of -0.6 ± 2.7 ‰. Plants analyzed here showed relatively smaller variability in δ13C than δ15N. Their average δ13C after suitable corrections for the Suess effect should be suitable as baseline for interpreting diets of Late Pleistocene herbivores that lived in eastern Beringia. Water availability, nitrogen availability, spacial differences and intra-plant variability are important controls on δ15N of herbaceous plants in the study area. The wider range of δ15N, the more numerous factors that affect nitrogen isotopic composition and their likely differences in the past, however, limit use of the modern N isotopic baseline for vegetation in paleodietary models for such ecosystems. That said, the positive correlation between foliar δ15N and N content shown for the modern plants could support use of plant δ15N as an index for plant N content and therefore forage quality. The modern N isotopic baseline cannot be applied directly to the past, but it is prerequisite to future efforts to detect shifts in N cycling and forage quality since the Late Pleistocene through comparison with fossil plants from the same region.

Stable nitrogen and carbon isotope (δ 15N and δ 13C) variability in shallow tropical Pacific soft coral and black coral taxa and implications for paleoceanographic reconstructions

NASA Astrophysics Data System (ADS)

Williams, Branwen; Grottoli, Andréa G.

2010-09-01

Soft corals and black corals are useful proxy tools for paleoceanographic reconstructions. However, most work has focused on deep-water taxa and few studies have used these corals as proxy organisms in shallow water (<200 m). To facilitate the use of stable nitrogen and carbon isotope (δ 15N and δ 13C) records from shallow-water soft coral and black coral taxa for paleoceanographic reconstructions, quantification of the inherent variability in skeletal isotope values between sites, across depth, and among taxa is needed. Here, skeletal δ 15N and δ 13C values were measured in multiple colonies from eleven genera of soft corals and two genera of black corals from across a depth transect (5-105 m) at two sites in Palau located in the tropical western Pacific Ocean. Overall, no difference in skeletal δ 15N and δ 13C values between sites was present. Skeletal δ 15N values significantly increased and δ 13C values decreased with depth. This is consistent with changes in isotope values of suspended particulate organic matter (POM) across the photic zone, suggesting that the primary food source to these corals is suspended POM and that the stable isotopic composition of POM controls the skeletal isotopic composition of these corals. Thus, to compare the isotope records of corals collected across a depth range in the photic zone, first order depth corrections of -0.013‰ m -1 and +0.023‰ m -1 are recommended for δ 15N and δ 13C, respectively. Average depth-corrected δ 15N values were similar between black corals and soft corals, indicating that corals in these orders feed at a similar trophic level. In contrast, average depth-corrected δ 13C values of black corals were significantly lower than that of soft corals, potentially resulting from metabolic processes associated with differing skeletal compositions among the orders (i.e., gorgonin vs. chitin based). Thus, a correction of +1.0‰ is recommended for black corals when comparing their δ 13C-based proxy records to soft corals. After correcting for both the depth and order effects, variability in δ 15N values among corals within each genera was low (standard deviation (SD) of the mean <±0.5‰), with the exception of Acanthorgorgia. The calculated SD of <±0.5‰ provides a first order guideline for the amount of variability that could be expected in a δ 15N record, and suggests that these corals may be useful for δ 15N-based paleoceanographic reconstructions. Variability in δ 13C values among corals within genera was also low (standard deviation of the mean <±0.5‰) with the exception of Rhipidipathes and Villogorgia. Similar to δ 15N, records from the genera studied here with the exception of Rhipidipathes and Villogorgia may be useful for δ 13C-based paleoceanographic reconstructions. Overall, using the recommendations developed here, stable isotope records from multiple sites, depths and taxa of these corals can be more rigorously compared.

Dense-gas properties in Arp 220 revealed by isotopologue lines

NASA Astrophysics Data System (ADS)

Wang, Junzhi; Zhang, Zhi-Yu; Zhang, Jiangshui; Shi, Yong; Fang, Min

2016-02-01

We present observations of isotopologue lines of dense-gas tracers at 3 mm and 1 mm towards the nearest ultra-luminous infrared galaxy Arp 220. The 3-mm and 1-mm observations were performed with the Institut de Radioastronomie Millimétrique 30-m telescope and the Atacama Pathfinder Experiment 12-m telescope, respectively. We detected H13CN and HN13C in 1-0 and 3-2, and HC15N 1-0, among which HC15N 1-0 and HN13C 1-0 are detected in Arp 220 for the first time. The H13CO+ 1-0 and 3-2 lines are unlikely to be detected because of the confusion of SiO lines. We find that the ratio of the line brightness temperatures of HN13C 3-2/1-0 is 2.4, which is significantly higher than that of H13CN 3-2/1-0 (0.73). This indicates that HN13C and HNC molecules are in denser regions than H13CN and HCN molecules. With the line ratio of H13CN 1-0 and HC15N 1-0, the 14N/15N ratio was estimated to be 440^{+140}_{-82}, which is larger than that of the local interstellar medium.

Large old trees influence patterns of delta13C and delta15N in forests.

PubMed

Weber, Pascale; Bol, Roland; Dixon, Liz; Bardgett, Richard D

2008-06-01

Large old trees are the dominant primary producers of native pine forest, but their influence on spatial patterns of soil properties and potential feedback to tree regeneration in their neighbourhood is poorly understood. We measured stable isotopes of carbon (delta(13)C) and nitrogen (delta(15)N) in soil and litter taken from three zones of influence (inner, middle and outer zone) around the trunk of freestanding old Scots pine (Pinus sylvestris L.) trees, to determine the trees' influence on below-ground properties. We also measured delta(15)N and delta(13)C in wood cores extracted from the old trees and from regenerating trees growing within their three zones of influence. We found a significant and positive gradient in soil delta(15)N from the inner zone, nearest to the tree centre, to the outer zone beyond the tree crown. This was probably caused by the higher input of (15)N-depleted litter below the tree crown. In contrast, the soil delta(13)C did not change along the gradient of tree influence. Distance-related trends, although weak, were visible in the wood delta(15)N and delta(13)C of regenerating trees. Moreover, the wood delta(15)N of small trees showed a weak negative relationship with soil N content in the relevant zone of influence. Our results indicate that large old trees control below-ground conditions in their immediate surroundings, and that stable isotopes might act as markers for the spatial and temporal extent of these below-ground effects. John Wiley & Sons, Ltd

Partial resolution of sources of n-alkanes in the saline portion of the Parachute Creek Member, Green River Formation (Piceance Creek Basin, Colorado)

NASA Technical Reports Server (NTRS)

Collister, J. W.; Lichtfouse, E.; Hieshima, G.; Hayes, J. M.

1994-01-01

Systematic variations in the 13C contents of individual extractable n-alkanes (C16-C29) can be modelled quantitatively and interpreted as indicating contributions from at least five distinct sources. These appear to be cyanobacterial (C16-C18, delta 13C = -37% vs PDB), phytoplanktonic (C16-C23, delta = -32%), chemoautotrophic bacterial (C20-C29, delta = -38%), phytoplanktonic or heterotrophic bacterial (C20-C29, delta = -30%), and vascular plants (C23-C29, delta = -29%). Hydrous pyrolysis of related kerogens yields large quantities of additional n-alkanes with different and much more uniform delta values. The latter materials are apparently derived from the thermolysis of aliphatic biopolymers whose presence in the Green River Oil Shale has been recognized visually.

Andrews AFB, Washington, District of Columbia. Revised Uniform Summary of Surface Weather Observations (RUSSWO). Parts A-F

DTIC Science & Technology

1974-03-14

boo Sol 15,71 2092 2573 c 1 15m17 2,6 6,9 ___ ___ 69j 493 13,1 17,0 2576 18-20 312 7,3 TO_ ___ __ 73056 ISO 20,21 2576 2102 2, o # 8,5 1397 to...PEES MEAN 2KT$ 1TCUA SUR AC W- .1 11 7.12 2 8-33-04 4 8.3 5 IND D T DIR.S SPEED NTAI# TAIO O es5 TE1mS 50 1 NNE CO3IT7O9 : NE ot ISO *6 ae , 4,* 7,4 E...2.33 34.40 41.47 48 • 56 % WINDDIR. IISPEED N , 2,. 2,1 lea ,4 6, 8,4 N E a’ log 0, t * 3 , alai NE ISO ] , a 1. 62 7.4 E E I t 11 1 1 4 a 7 , 7 1

The complete set of spin observables for the (13)C(polarized proton, polarized neutron)(13)N and (15)N(polarized proton, polarized neutron)(15)O reactions

NASA Astrophysics Data System (ADS)

Du, Qun Qun

1998-12-01

The 13C(p,n)13N and 15N(p,n)15O reactions have been a puzzle for more than ten years. The ground state transitions are Jπ=1/2- to Jπ=1/2-. These are 'mixed' transitions because they can involve quantum number changes either (/Delta T=1,/ /Delta J=0,/ /Delta/pi=0,/ /Delta S=0), or (/Delta T=1,/ /Delta J=1,/ /Delta/pi=0,/ /Delta S=1); these quantum number changes are refered to as 'Fermi' and 'Gamow-Teller' respectively. Because the quantum number changes are the same as for Fermi and Gamow-Teller beta decay. From the systematics of (p,n) and (n,p) reactions on pure Fermi transitions (e.g. 0 + to 0+) and pure Gamow-Teller transitions (e.g. 0+ to 1+), calibrations have been established of cross section per unit B(F) or unit B(GT), where 'B' refers to doubly reduced matrix elements extracted from beta decay. However, cross sections for the 13C(p,n)13N(g.s.) and 15N(p,n)15O(g.s.) reactions are substantially larger than one would then predict from the known B(F)s and B(GT)s for these transitions. To explore this anomaly, spin observables were used to extract separately the Fermi and Gamow-Teller cross sections for these reactions. To acquire the complete sets of polarization- transfer observables, a new neutron polarimeter was designed, built, commissioned and calibrated. This polarimeter, call the '2π polarimeter' because of its complete azimuthal coverage for scattered neutrons, has very good position and timing resolution (354 ps). The complete sets of spin-transfer coefficients Dij for 13C(p,n)13N (at 0o , 5.5o , and 11o ) and 15N(p,n)15O (at 0o ) at 135 MeV were measured. Following the formalism of Ichimura and Kawahigashi, we extracted the spin-longitudinal, and spin-transverse and spin-independent responses D0,/ Dq,/ Dn and Dp from the measured Dijs. The F and GT fractions of the (p,n) cross sections are then extracted as f F=D0 and fGT=Dn+Dp+Dq=1- d0. Values of Dk for both the 13C(p,n)13N(g.s) and 15N(p,n)15O(g.s.) were extracted. From these responses, we extracted. From these responses, we extracted fGT and fF, the GT and Fermi fractions for these transitions in a model-independent fashion. Values for FGT extracted by another group at other beam energies in a model-dependent manner from DNN/sp' alone, are in good agreement with our model-independent values. These results were also compared with the empirical energy-dependence of ratio of σtau to τ strength for the (p,n) reaction extracted primarily from even-A targets. Our measured values of fGT are typically 10% larger than predicted from β-decay matrix elements and even-A (p,n) systematics. Since the cross sections for these transitions are anomalously large, this suggests that the GT strength in these transitions is ~50% larger than expected from β-decay and even-A (p,n) systematics. The measured values of Dk and cross sections for the 13C(p,n)13N(g.s) transition were compared with the DWIA calculations, where modest agreement was achieved.

The metabolic fate of doubly stable isotope labelled heat-killed Lactobacillus johnsonii in humans.

PubMed

Wutzke, K D; Berg, D; Haffner, D

2008-02-01

In this study, heat-killed Lactobacillus johnsonii (La1), doubly labelled with (13)C and (15)N (hk-dlLa1), was used to follow the metabolic fate after oral administration in humans. Experimental study. University of Rostock, Children's Hospital, Research Laboratory. Ten healthy adults aged 23-26 years. The subjects received 74.6 mg/kg body weight hk-dlLa1 and 10 g alpha-D-raffinose together with breakfast. A sample of venous blood was taken after 2 h. Expired air samples were taken over 14 h, whereas urine and faeces were collected over a period of 48 h. (13)C- and (15)N-enrichments were measured by isotope ratio mass spectrometry. Hydrogen concentrations were measured by electrochemical detection. The orocaecal transit time (OCTT) was reached after 3.4 h. After 2 h, (13)C- and (15)N-enrichment of fibrinogen amounted to 2 and 25 p.p.m. excess, respectively. The (13)CO(2)-exhalation amounted to 9.2% of the ingested dose. The urinary excretion of (13)C and (15)N was 2.1 and 10.4% of the ingested dose, respectively, whereas the faecal excretion was 47.9 and 43.7% of the ingested dose, respectively. In comparison to OCTT of 3.4 h, both stable isotopes appear after 30 min in breath and urine, indicating that hk-dlLa1 is rapidly digested in the small bowel before reaching the caecum. This is confirmed by (13)C-and (15)N-enrichments of blood plasma fractions. The ingestion of hk-dlLa1 led to a (13)C- and (15)N-excretion of 59.2 and 54.1% of the ingested dose, respectively, of both stable isotopes.

Stable Carbon and Nitrogen Isotopes in a Peat Profile Are Influenced by Early Stage Diagenesis and Changes in Atmospheric CO(2) and N Deposition.

PubMed

Esmeijer-Liu, Alice J; Kürschner, Wolfram M; Lotter, André F; Verhoeven, Jos T A; Goslar, Tomasz

2012-06-01

In this study, we test whether the δ(13)C and δ(15)N in a peat profile are, respectively, linked to the recent dilution of atmospheric δ(13)CO(2) caused by increased fossil fuel combustion and changes in atmospheric δ(15)N deposition. We analysed bulk peat and Sphagnum fuscum branch C and N concentrations and bulk peat, S. fuscum branch and Andromeda polifolia leaf δ(13)C and δ(15)N from a 30-cm hummock-like peat profile from an Aapa mire in northern Finland. Statistically significant correlations were found between the dilution of atmospheric δ(13)CO(2) and bulk peat δ(13)C, as well as between historically increasing wet N deposition and bulk peat δ(15)N. However, these correlations may be affected by early stage kinetic fractionation during decomposition and possibly other processes. We conclude that bulk peat stable carbon and nitrogen isotope ratios may reflect the dilution of atmospheric δ(13)CO(2) and the changes in δ(15)N deposition, but probably also reflect the effects of early stage kinetic fractionation during diagenesis. This needs to be taken into account when interpreting palaeodata. There is a need for further studies of δ(15)N profiles in sufficiently old dated cores from sites with different rates of decomposition: These would facilitate more reliable separation of depositional δ(15)N from patterns caused by other processes. ELECTRONIC SUPPLEMENTARY MATERIAL: The online version of this article (doi:10.1007/s11270-011-1001-8) contains supplementary material, which is available to authorized users.

Food-web structure and trophodynamics of mesopelagic-suprabenthic bathyal macrofauna of the Algerian Basin based on stable isotopes of carbon and nitrogen

NASA Astrophysics Data System (ADS)

Fanelli, E.; Cartes, J. E.; Rumolo, P.; Sprovieri, M.

2009-09-01

The trophodynamics of mesopelagic (macrozooplankton/micronekton) and benthic boundary layer (suprabenthos=hyperbenthos) faunas from the Algerian Basin were characterized on a seasonal scale through stable carbon and nitrogen isotopic analyses of a total of 34 species and two broad taxa (Copepoda and Cumacea). This is the first study simultaneously focused on trophodynamics of deep-sea zooplankton and suprabenthos. Samples were collected southeast of Mallorca (Algerian Basin, Western Mediterranean), on the continental slope close to Cabrera Archipelago, at 650-780 m depths, ca. bi-monthly between August 2003 and June 2004. Mean δ 13C values of suprabenthos ranged from -21.1‰ ( Munnopsurus atlanticus) to -16.7‰ ( Cyclaspis longicaudata). Values of δ 15N ranged from 2.8‰ ( Lepechinella manco) to 9.9‰ (larvae of Gnathia sp.). The stable isotope ratios of suprabenthic fauna displayed a continuum of values, confirming a wide spectrum of feeding guilds (from filter feeders/surface deposit feeders to predators). According to the available information on diets for suprabenthic species, the highest annual mean δ 15N values were found for the hematophagous isopod Gnathia sp. parasite on fish (represented by Praniza larvae) and carnivorous amphipods (e.g. Rhachotropis spp., Nicippe tumida) consuming copepods, and the lowest δ 15N values were found for two cumaceans ( Cyclaspis longicaudata and Platysympus typicus) feeding on detritus. Assuming a 15N-enrichment factor of 2.5‰ and deposit feeders as baseline, we found three trophic levels in suprabenthic food webs. δ 13C ranges were particularly wide among deposit feeders (ranging from -21.8% to -17.3‰) and omnivores (from -20.5% to -18.8‰), suggesting exploitation of particulate organic matter (POM) of different characteristics. Our isotopic analyses revealed lower ranges of δ 13C and δ 15N for macrozooplankton/micronekton, compared with suprabenthos. δ 13C values of zooplankton taxa ranged from -21.1‰ (the hyperiid Phrosina semilunata) to -19.9‰ (the decapod Pasiphaea multidentata), while δ 15N values ranged from 3.9‰ ( P. semilunata) to 7.5‰ ( P. multidentata). Among zooplankton, more enriched δ 15N values were found among carnivores (e.g. the fish Cyclothone spp. and Pasiphaea multidentata) preying on copepods, hyperiids, euphausiids and small fish. The lowest δ 15N values were found for hyperiids that feed on the mucus nets of salps (e.g. Vibilia armata). After contrasting isotope analysis with dietary data, we conclude there were two trophic levels among zooplankton/micronekton. Strong correlation between the mean annual δ 15N and δ 13C values was found for zooplankton ( R2=0.7), but not for suprabenthos, which suggests a single source of carbon for plankton. We found a general seasonal trend for δ 13C enrichment from late autumn (November) to late winter-spring (February-April) for both suprabenthos and zooplankton. The δ 13C enrichment in February-April was correlated in zooplankton with higher surface chlorophyll a concentration 1 month before sampling. As evidenced by δ 13C-δ 15N correlations, the response of zooplankton to the peak of surface primary production was almost immediate (an increase of δ 13C-δ 15N correlations in February), and stronger than for suprabenthos. The response among suprabenthos was weak, with slight increase in δ 13C-δ 15N relationships in April-June.

CARBON-RICH PRESOLAR GRAINS FROM MASSIVE STARS: SUBSOLAR {sup 12}C/{sup 13}C AND {sup 14}N/{sup 15}N RATIOS AND THE MYSTERY OF {sup 15}N

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

Pignatari, M.; Zinner, E.; Hoppe, P.

2015-08-01

Carbon-rich grains with isotopic anomalies compared to the Sun are found in primitive meteorites. They were made by stars, and carry the original stellar nucleosynthesis signature. Silicon carbide grains of Type X and C and low-density (LD) graphites condensed in the ejecta of core-collapse supernovae. We present a new set of models for the explosive He shell and compare them with the grains showing {sup 12}C/{sup 13}C and {sup 14}N/{sup 15}N ratios lower than solar. In the stellar progenitor H was ingested into the He shell and not fully destroyed before the explosion. Different explosion energies and H concentrations aremore » considered. If the supernova shock hits the He-shell region with some H still present, the models can reproduce the C and N isotopic signatures in C-rich grains. Hot-CNO cycle isotopic signatures are obtained, including a large production of {sup 13}C and {sup 15}N. The short-lived radionuclides {sup 22}Na and {sup 26}Al are increased by orders of magnitude. The production of radiogenic {sup 22}Ne from the decay of {sup 22}Na in the He shell might solve the puzzle of the Ne-E(L) component in LD graphite grains. This scenario is attractive for the SiC grains of type AB with {sup 14}N/{sup 15}N ratios lower than solar, and provides an alternative solution for SiC grains originally classified as nova grains. Finally, this process may contribute to the production of {sup 14}N and {sup 15}N in the Galaxy, helping to produce the {sup 14}N/{sup 15}N ratio in the solar system.« less

Carbon-rich presolar grains from massive stars. Subsolar 12 C/ 13 C and 14 N/ 15 N ratios and the mystery of 15 N

DOE PAGES

Pignatari, M.; Zinner, E.; Hoppe, P.; ...

2015-07-30

We compared carbon-rich grains with isotopic anomalies to the Sun are found in primitive meteorites. They were made by stars, and carry the original stellar nucleosynthesis signature. Silicon carbide grains of Type X and C and low-density (LD) graphites condensed in the ejecta of core-collapse supernovae. Furthermore, we present a new set of models for the explosive He shell and compare them with the grains showing 12C/ 13C and 14N/ 15N ratios lower than solar. In the stellar progenitor H was ingested into the He shell and not fully destroyed before the explosion. All of the explosion energies and Hmore » concentrations are considered. If the supernova shock hits the He-shell region with some H still present, the models can reproduce the C and N isotopic signatures in C-rich grains. Hot-CNO cycle isotopic signatures are obtained, including a large production of 13C and 15N. The short-lived radionuclides 22Na and 26Al are increased by orders of magnitude. The production of radiogenic 22Ne from the decay of 22Na in the He shell might solve the puzzle of the Ne-E(L) component in LD graphite grains. This scenario is attractive for the SiC grains of type AB with 14N/ 15N ratios lower than solar, and provides an alternative solution for SiC grains originally classified as nova grains. Finally, this process may contribute to the production of 14N and 15N in the Galaxy, helping to produce the 14N/ 15N ratio in the solar system.« less

Urea and lipid extraction treatment effects on δ(15)N and δ(13)C values in pelagic sharks.

PubMed

Li, Yunkai; Zhang, Yuying; Hussey, Nigel E; Dai, Xiaojie

2016-01-15

Stable isotope analysis (SIA) provides a powerful tool to investigate diverse ecological questions for marine species, but standardized values are required for comparative assessments. For elasmobranchs, their unique osmoregulatory strategy involves retention of (15)N-depleted urea in body tissues and this may bias δ(15)N values. This may be a particular problem for large predatory species, where δ(15)N discrimination between predator and consumed prey can be small. We evaluated three treatments (deionized water rinsing [DW], chloroform/methanol [LE] and combined chloroform/methanol and deionized water rinsing [LE+DW]) applied to white muscle tissue of 125 individuals from seven pelagic shark species to (i) assess urea and lipid effects on stable isotope values determined by IRMS and (ii) investigate mathematical normalization of these values. For all species examined, the δ(15)N values and C:N ratios increased significantly following all three treatments, identifying that urea removal is required prior to SIA of pelagic sharks. The more marked change in δ(15)N values following DW (1.3 ± 0.4‰) and LE+DW (1.2 ± 0.6‰) than following LE alone (0.7 ± 0.4‰) indicated that water rinsing was more effective at removing urea. The DW and LE+DW treatments lowered the %N values, resulting in an increase in C:N ratios from the unexpected low values of <2.6 in bulk samples to ~3.1 ± 0.1, the expected value of protein. The δ(13)C values of all species also increased significantly following LE and LE+DW treatments. Given the mean change in δ(15)N(1.2 ± 0.6‰) and δ(13)C values (0.7 ± 0.4‰) across pelagic shark species, it is recommended that muscle tissue samples be treated with LE+DW to efficiently extract both urea and lipids to standardize isotopic values. Mathematical normalization of urea and lipid-extracted δ(15)N(LE+DW) and δ(13)C(LE+DW) values using the lipid-extracted δ(15)N(LE) and δ(13)C(LE) data were established for all pelagic shark species. Copyright © 2015 John Wiley & Sons, Ltd.

[Injectable hospital preparation of valine labeled with the carbon 13 and nitrogen 15 (5 mg/mL) for a clinical trial on the brain tumor metabolism: Pharmaceutical control of active pharmaceutical ingredient and stability study of the finished product].

PubMed

Tall, M L; Diouf, E; Filali, S; Sauvinet, V; Laleye, D; Dhelens, C; Salmon, D; Gabert, L; Nugue, G; Sandre-Balester, C; Berger, F; Pirot, F; Pivot, C

2015-09-01

The L-Valine labeled (L-[U-(13)C,(15)N] Val) is a stable isotopic tracer administered by parenteral route within the framework of a new clinical research program concerning the brain tumor metabolism. To meet regulatory requirements and have ready to use solution with an expiration date, a pharmaceutical control of active pharmaceutical ingredient followed by stability study of hospital preparation were realised. After the pharmaceutical control of the L-[U-(13)C,(15)N] Val, the hospital preparation was prepared according to the good manufacturing preparation. Prepared bottles were stored at 5°C±3°C and 25°C±2°C for six months. The stability of the preparation was determined by physico-chemical controls (pH, osmolality, sub-visible particles, L-[U-(13)C,(15)N] Val concentration, sodium concentration, isotopic enrichment) and microbiological (bacterial endotoxin and sterility). Concentrations of L-[U-(13)C, (15)N] Val and sodium does not significantly decrease during the stability study. In parallel, no change in pH and osmolality were highlighted. Isotopic enrichment higher than 99.9% reflected the stability of labeling of L-valine molecule. The sub-visible particles, the bacterial endotoxin and sterility were in accordance with the European Pharmacopoeia attesting limpidity, apyrogenicity and sterility of this injectable preparation. The stability of this hospital preparation of L-[U-(13)C, (15)N] Val has been demonstrated for six months at 5°C±3°C and 25°C±2°C, ensuring a parenteral administration as part of the clinical trial. Copyright © 2015 Elsevier Masson SAS. All rights reserved.

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...

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

The Role of Anthropogenic Activity and Climate on δ15N Values of Cave Bat Guano

NASA Astrophysics Data System (ADS)

Cleary, D. M.; Onac, B. P.; Forray, F. L.; Wynn, J. G.

2016-12-01

Interest in the use of bat guano, a paleoclimate and paleoenvironmental resource, has rapidly increased over the past decade. However, to this point the utility of the δ15N values of guano as a potential proxy remains poorly understood. In contrast to the preservation of the original carbon isotopic composition of guano, δ15N values have the potential to be altered as a result of processes of nitrogen (N) cycling such as denitrification. However, the probability of N loss is relatively diminished in younger guano. Here we present a 1.5 m guano core from Zidită Cave in western Romania that began accumulating at ca. 913 ± 30 yr BP. To determine the utility of N isotopes in guano studies, the δ15N time-series was compared to δ13C time series and pollen records of the same core to determine if the environmental impact (pollen) or water availability (δ13C values) has an effect on N cycling. Unlike to previous guano studies, the N content in the core is nearly constant (%N > 9 %) for over 1 m of the core, indicating limited diagenesis. Although major changes in anthropogenic activities may have influenced some δ15N variation, some inconsistencies suggest this is not the primary controller. However, the correlation between δ15N and δ13C values (p < 0.01) in this C3-plant dominated ecosystem has been interpreted to reflect variation driven largely by water availability. Wetter periods indicated by lower δ13C values correspond with higher δ15N values of guano. These results indicate that when the area surrounding the Zidită Cave receives an increase in rainfall the N-cycle becomes more open with a decreased rate of denitrification or other processes that accumulate 15N in the soil reservoir. A 10-year instrumental precipitation dataset agrees with the relationship found between δ13C and δ15N time series. These results suggest that guano δ15N values from Zidită Cave are a suitable proxy record of climate for this type of system, but we emphasize that this coupling of processes may not be universal. Over the past 60 years the δ15N values have decreased by 5.5 ‰, indicating that the N-cycle has been approaching a more conservative state in response to drier conditions. From this study it is clear that the potential utility of δ15N of guano (climate and state of the N-cycle) may have previously been overlooked.

Carbon and nitrogen systematics in nitrogen-rich, ultradeep diamonds from Sao Luiz, Brazil

NASA Astrophysics Data System (ADS)

Navon, Oded; Stachel, Thomas; Stern, Richard A.; Harris, Jeffrey W.

2018-05-01

Three diamonds from Sao Luiz, Brazil carrying nano- and micro-inclusions of molecular δ-N2 that exsolved at the base of the transition zone were studied for their C and N isotopic composition and the concentration of N utilizing SIMS. The diamonds are individually uniform in their C isotopic composition and most spot analyses yield δ13C values of -3.2 ± 0.1‰ (ON-SLZ-390) and - 4.7 ± 0.1‰ (ON-SLZ-391 and 392). Only a few analyses deviate from these tight ranges and all fall within the main mantle range of -5 ± 3‰. Most of the N isotope analyses also have typical mantle δ15N values (-6.6 ± 0.4‰, -3.6 ± 0.5‰ and - 4.1 ± 0.6‰ for ON-SLZ-390, 391 and 392, respectively) and are associated with high N concentrations of 800-1250 atomic ppm. However, some N isotopic ratios, associated with low N concentrations (<400 ppm) and narrow zones with bright luminescence are distinctly above the average, reaching positive δ15N values. These sharp fluctuations cannot be attributed to fractionation. They may reflect arrival of new small pulses of melt or fluid that evolved under different conditions. Alternatively, they may result from fractionation between different growth directions, so that distinct δ15N values and N concentrations may form during diamond growth from a single melt/fluid. Other more continuous variations, in the core of ON-SLZ-390 or the rim of ON-SLZ-392 may be the result of Rayleigh fractionation or mixing.

Spectral density mapping at multiple magnetic fields suitable for 13C NMR relaxation studies

NASA Astrophysics Data System (ADS)

Kadeřávek, Pavel; Zapletal, Vojtěch; Fiala, Radovan; Srb, Pavel; Padrta, Petr; Přecechtělová, Jana Pavlíková; Šoltésová, Mária; Kowalewski, Jozef; Widmalm, Göran; Chmelík, Josef; Sklenář, Vladimír; Žídek, Lukáš

2016-05-01

Standard spectral density mapping protocols, well suited for the analysis of 15N relaxation rates, introduce significant systematic errors when applied to 13C relaxation data, especially if the dynamics is dominated by motions with short correlation times (small molecules, dynamic residues of macromolecules). A possibility to improve the accuracy by employing cross-correlated relaxation rates and on measurements taken at several magnetic fields has been examined. A suite of protocols for analyzing such data has been developed and their performance tested. Applicability of the proposed protocols is documented in two case studies, spectral density mapping of a uniformly labeled RNA hairpin and of a selectively labeled disaccharide exhibiting highly anisotropic tumbling. Combination of auto- and cross-correlated relaxation data acquired at three magnetic fields was applied in the former case in order to separate effects of fast motions and conformational or chemical exchange. An approach using auto-correlated relaxation rates acquired at five magnetic fields, applicable to anisotropically moving molecules, was used in the latter case. The results were compared with a more advanced analysis of data obtained by interpolation of auto-correlated relaxation rates measured at seven magnetic fields, and with the spectral density mapping of cross-correlated relaxation rates. The results showed that sufficiently accurate values of auto- and cross-correlated spectral density functions at zero and 13C frequencies can be obtained from data acquired at three magnetic fields for uniformly 13C -labeled molecules with a moderate anisotropy of the rotational diffusion tensor. Analysis of auto-correlated relaxation rates at five magnetic fields represents an alternative for molecules undergoing highly anisotropic motions.

Agents Overcoming Resource Independent Scaling Threats (AORIST)

DTIC Science & Technology

2004-10-01

20 Table 8: Tilted Consumer Preferences Experiment (m=8, N=61, G=2, C=60, Mean over 13 experiments...probabilities. Non-uniform consumer preferences create a new potential for sub-optimal system performance and thus require an additional adaptive...distribu- tion of the capacities across the sup- plier population must match the non- uniform consumer preferences . The second plot in Table 8

Effects of climate on deer bone δ15N and δ13C: Lack of precipitation effects on δ15N for animals consuming low amounts of C 4 plants

NASA Astrophysics Data System (ADS)

Cormie, A. B.; Schwarcz, H. P.

1996-11-01

We have examined the relationship of bone collagen δ15N and δ13C to climatic variables, humidity, temperature, and amount of precipitation using fifty-nine specimens of North American white-tailed deer ( Odocoileus virginianus) from forty-six different locations. In previous studies of African mammals there was a significant correlation between bone collagen δ15N and local amount of precipitation. Results presented here similarly show an increase in δ15N with decreasing amount of precipitation but only for 25% of the animals, namely those consuming more than 10% C 4 plants. These animals also exhibited a significant correlation between δ13C and temperature which mirrors previous observations for grasses suggesting that these deer consume grasses during times of population and nutrient stress. In contrast, even in dry areas containing high proportions of C 4 grasses, the majority of the deer had consumed low amounts of C 4 plants and these deer did not have δ15N which correlate with amount of precipitation. Only when deer deviated from their normal feeding pattern by consuming C 4 plants or grasses did their δ15N correlate with amount of rainfall. For these animals, consumption of C 4 plants or grasses may signal conditions of water and nutrient stress. An increase in δ15N of bone collagen may result from combined effects from excretion of concentrated urine (to conserve water) and increased internal recycling of nitrogen (to conserve nitrogen).

Variation in δ15N and δ13C values of forages for Arctic caribou: Effects of location, phenology and simulated digestion

USGS Publications Warehouse

Vansomeren, Lindsey L.; Barboza, Perry S.; Gustine, David D.; Bret-Harte, M. Syndonia

2017-01-01

RationaleThe use of stable isotopes for dietary estimates of wildlife assumes that there are consistent differences in isotopic ratios among diet items, and that the differences in these ratios between the diet item and the animal tissues (i.e., fractionation) are predictable. However, variation in isotopic ratios and fractionation of δ13C and δ15N values among locations, seasons, and forages are poorly described for arctic herbivores especially migratory species such as caribou (Rangifer tarandus).MethodsWe measured the δ13C and δ15N values of seven species of forage growing along a 200-km transect through the range of the Central Arctic caribou herd on the North Slope of Alaska over 2 years. We compared forages available at the beginning (May; n = 175) and the end (n = 157) of the growing season (September). Purified enzymes were used to measure N digestibility and to assess isotopic fractionation in response to nutrient digestibility during simulated digestion.ResultsValues for δ13C declined by 1.38 ‰ with increasing latitude across the transect, and increased by 0.44 ‰ from the beginning to the end of the season. The range of values for δ15N was greater than that for δ13C (13.29 vs 5.60 ‰). Differences in values for δ13C between graminoids (Eriophorum and Carex spp.) and shrubs (Betula and Salix spp.) were small but δ15N values distinguished graminoids (1.87 ± 1.02 ‰) from shrubs (−2.87 ± 2.93 ‰) consistently across season and latitude. However, undigested residues of forages were enriched in 15N when the digestibility of N was less than 0.67.ConclusionsAlthough δ15N values can distinguish plant groups in the diet of arctic herbivores, variation in the digestibility of dietary items may need to be considered in applying fractionation values for 15N to caribou and other herbivores that select highly digestible items (e.g. forbs) as well as heavily defended plants (e.g. woody browse).

Drying method has no substantial effect on δ(15)N or δ(13)C values of muscle tissue from teleost fishes.

PubMed

Bessey, Cindy; Vanderklift, Mathew A

2014-02-15

Stable isotope analysis (SIA) is a powerful tool in many fields of research that enables quantitative comparisons among studies, if similar methods have been used. The goal of this study was to determine if three different drying methods commonly used to prepare samples for SIA yielded different δ(15)N and δ(13)C values. Muscle subsamples from 10 individuals each of three teleost species were dried using three methods: (i) oven, (ii) food dehydrator, and (iii) freeze-dryer. All subsamples were analysed for δ(15)N and δ(13)C values, and nitrogen and carbon content, using a continuous flow system consisting of a Delta V Plus mass spectrometer and a Flush 1112 elemental analyser via a Conflo IV universal interface. The δ(13)C values were normalized to constant lipid content using the equations proposed by McConnaughey and McRoy. Although statistically significant, the differences in δ(15)N values between the drying methods were small (mean differences ≤0.21‰). The differences in δ(13)C values between the drying methods were not statistically significant, and normalising the δ(13)C values to constant lipid content reduced the mean differences for all treatments to ≤0.65‰. A statistically significant difference of ~2% in C content existed between tissues dried in a food dehydrator and those dried in a freeze-dryer for two fish species. There was no significant effect of fish size on the differences between methods. No substantial effect of drying method was found on the δ(15)N or δ(13)C values of teleost muscle tissue. Copyright © 2013 John Wiley & Sons, Ltd.

Hyperpolarized 13 C,15 N2 -Urea MRI for assessment of the urea gradient in the porcine kidney.

PubMed

Hansen, Esben S S; Stewart, Neil J; Wild, Jim M; Stødkilde-Jørgensen, Hans; Laustsen, Christoffer

2016-12-01

A decline in cortico-medullary osmolality gradient of the kidney may serve as an early indicator of pathological disruption of the tubular reabsorption process. The purpose of this study was to investigate the feasibility of hyperpolarized 13 C, 15 N 2 -urea MRI as a biomarker of renal function in healthy porcine kidneys resembling the human physiology. Five healthy female Danish domestic pigs (weight 30 kg) were scanned at 3 Tesla (T) using a 13 C 3D balanced steady-state MR pulse sequence following injection of hyperpolarized 13 C, 15 N 2 -urea via a femoral vein catheter. Images were acquired at different time points after urea injection, and following treatment with furosemide. A gradient in cortico-medullary urea was observed with an intramedullary accumulation 75 s after injection of hyperpolarized 13 C, 15 N 2 -urea, whereas images acquired at earlier time points postinjection were dominated by cortical perfusion. Furosemide treatment resulted in an increased urea accumulation in the cortical space, leading to a reduction of the medullary-to-cortical signal ratio of 49%. This study demonstrates that hyperpolarized 13 C, 15 N 2 -urea MRI is capable of identifying the intrarenal accumulation of urea and can differentiate acute renal functional states in multipapillary kidneys, highlighting the potential for human translation. Magn Reson Med 76:1895-1899, 2016. © 2016 International Society for Magnetic Resonance in Medicine. © 2016 International Society for Magnetic Resonance in Medicine.

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

Treesearch

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

2000-01-01

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

Elucidating the trophodynamics of four coral reef fishes of the Solomon Islands using δ15N and δ13C

NASA Astrophysics Data System (ADS)

Greenwood, N. D. W.; Sweeting, C. J.; Polunin, N. V. C.

2010-09-01

Size-related diet shifts are important characteristics of fish trophodynamics. Here, body size-related changes in muscle δ15N and δ13C of four coral reef fishes, Acanthurus nigrofuscus (herbivore), Chaetodon lunulatus (corallivore) , Chromis xanthura (planktivore) and Plectropomus leopardus (piscivore) were investigated at two locations in the Solomon Islands. All four species occupied distinct isotopic niches and the concurrent δ13C' values of C. xanthura and P. leopardus suggested a common planktonic production source. Size-related shifts in δ15N, and thus trophic level, were observed in C. xanthura, C. lunulatus and P. leopardus, and these trends varied between location, indicating spatial differences in trophic ecology. A literature review of tropical fishes revealed that positive δ15N-size trends are common while negative δ15N-size trends are rare. Size-δ15N trends fall into approximately equal groups representing size-based feeding within a food chain, and that associated with a basal resource shift and occurs in conjunction with changes in production source, indicated by δ13C. The review also revealed large scale differences in isotope-size trends and this, combined with small scale location differences noted earlier, highlights a high degree of plasticity in the reef fishes studied. This suggests that trophic size analysis of reef fishes would provide a productive avenue to identify species potentially vulnerable to reef impacts as a result of constrained trophic behaviour.

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

PubMed

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

2018-05-01

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

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

PubMed

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

2013-05-01

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

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

PubMed

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

2009-09-01

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

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 the first organic nitrogen stable isotope reference materials for GC-IRMS that are available with different delta15N values. Comparative delta13C and delta15N on-line EA-IRMS data from 14 volunteering laboratories document the usefulness and reliability of acetanilides and ureas as EA-IRMS reference materials. Copyright 2009 John Wiley & Sons, Ltd.

Diet discrimination factors are inversely related to δ15 N and δ13C values of food for fish under controlled conditions.

PubMed

Dennis, Caroline A; Macneil, M Aaron; Rosati, Jennifer Y; Pitcher, Trevor E; Fisk, Aaron T

2010-12-30

A recent literature review reported negative relationships between diet discrimination factors (DDFs = X(fish) - X(food) ; X = δ(15) N or δ(13) C) and the values of δ(15) N and δ(13) C in the food of wild organisms but there has been no laboratory-based confirmation of these relationships to date. Laboratory reared guppies (Poecilia reticulata) fed a series of diets with a range of δ(13) C (-22.9 to -6.6‰) and δ(15) N (6.5 to 1586‰) values were used to magnify diet-tissue dynamics in order to calculate DDFs once the fish had achieved equilibrium with each of the diets. Values of DDFs range widely for δ(15) N (7.1 to -849‰) and δ(13) C (1.1 to -7.0‰) and showed a strong negative correlation with the stable isotope value in the food for δ(15) N (slope = -0.59 ± 0.02, r(2)  = 0.95) and δ(13) C (slope = -0.56 ± 0.02, r(2)  = 0.94). Based on these relationships, the magnitude of DDF change over environmentally relevant values of δ(15) N or δ(13) C would be significant and could confound the interpretation of stable isotopes in the environment. Using highly enriched experimental diets, our study adds to a growing number of studies that undermine the consistent trophic enrichment paradigm with results that demonstrate the currently poor mechanistic understanding of how DDFs arise. The results of our study highlight that the magnitude of the stable isotope values in prey must be considered when choosing DDF values. Future laboratory studies should therefore be directed at uncovering the mechanistic basis of DDFs and, like others before, we recommend the determination of diet-dependent DDFs under laboratory conditions before modeling dietary proportions or calculating trophic positions. Copyright © 2010 John Wiley & Sons, Ltd.

Nitrogen and carbon isotopic dynamics of subarctic soils and plants in southern Yukon Territory and its implications for paleoecological and paleodietary studies

PubMed Central

Longstaffe, Fred J.; Zazula, Grant; Bennett, Bruce

2017-01-01

We examine here the carbon and nitrogen isotopic compositions of bulk soils (8 topsoil and 7 subsoils, including two soil profiles) and five different plant parts of 79 C3 plants from two main functional groups: herbs and shrubs/subshrubs, from 18 different locations in grasslands of southern Yukon Territory, Canada (eastern shoreline of Kluane Lake and Whitehorse area). The Kluane Lake region in particular has been identified previously as an analogue for Late Pleistocene eastern Beringia. All topsoils have higher average total nitrogen δ15N and organic carbon δ13C than plants from the same sites with a positive shift occurring with depth in two soil profiles analyzed. All plants analyzed have an average whole plant δ13C of −27.5 ± 1.2 ‰ and foliar δ13C of –28.0 ± 1.3 ‰, and average whole plant δ15N of −0.3 ± 2.2 ‰ and foliar δ15N of –0.6 ± 2.7 ‰. Plants analyzed here showed relatively smaller variability in δ13C than δ15N. Their average δ13C after suitable corrections for the Suess effect should be suitable as baseline for interpreting diets of Late Pleistocene herbivores that lived in eastern Beringia. Water availability, nitrogen availability, spacial differences and intra-plant variability are important controls on δ15N of herbaceous plants in the study area. The wider range of δ15N, the more numerous factors that affect nitrogen isotopic composition and their likely differences in the past, however, limit use of the modern N isotopic baseline for vegetation in paleodietary models for such ecosystems. That said, the positive correlation between foliar δ15N and N content shown for the modern plants could support use of plant δ15N as an index for plant N content and therefore forage quality. The modern N isotopic baseline cannot be applied directly to the past, but it is prerequisite to future efforts to detect shifts in N cycling and forage quality since the Late Pleistocene through comparison with fossil plants from the same region. PMID:28813532

Spatial and temporal expression of vegetation and atmospheric variability from stable carbon and nitrogen isotope analysis of bat guano in the southern United States

NASA Astrophysics Data System (ADS)

Wurster, Christopher M.; McFarlane, Donald A.; Bird, Michael I.

2007-07-01

Stable isotopes of faeces contain information related to the animals feeding ecology. The use of stable isotope values from subfossil faeces as a palaeoenvironmental indicator depends on how faithfully the animal records their local environment. Here we present insectivorous bat guano δ 13C and δ 15N values from a precipitation gradient across the southern United States and northern Mexico to compare with local vegetation and climate. We find δ 13C values to be an excellent predictor of expected C 4/CAM vegetation, indicating that the bats are non-selective in their diet. Moreover, we find bat guano δ 13C values to be strongly correlated with summer precipitation amount and winter precipitation ratio. We also find evidence for a significant relationship with mean annual temperature. In general, we do not find δ 15N values to be related to any parameters along the climatic gradient we examined. Additionally, we measured δ 13C and δ 15N values of bulk guano deposited annually from 1968 to 1987 in a varved guano deposit at Eagle Creek Cave, Arizona. Neither δ 13C nor δ 15N values were significantly related to various local meteorological variables; however, we found δ 13C values of guano to be significantly related to drought and to the North American Monsoon indicating bat guano δ 13C values preserve an interpretable record of large-scale atmospheric variability.

Isotopic fractionation of nitrogen and carbon in Paleoarchean cherts from Pilbara craton, Western Australia: Origin of 15N-depleted nitrogen

NASA Astrophysics Data System (ADS)

Pinti, Daniele L.; Hashizume, Ko; Sugihara, Akiyo; Massault, Marc; Philippot, Pascal

2009-07-01

Nitrogen and carbon isotopic compositions, together with mineralogy and trace element geochemistry, were studied in a few kerogen-rich Paleoarchean cherts, a barite and a dolomitic stromatolite belonging to the eastern (Dixon Island Formation) and western (Dresser and Strelley Pool Chert Formations; North Pole Dome and Marble Bar) terranes of Pilbara Craton, Western Australia. The aim of the study was to search for 15N-depleted isotopic signatures, often found in kerogens of this period, and explain the origin of these anomalies. Trace elements suggest silica precipitation by hydrothermal fluids as the main process of chert formation with a contamination from volcanoclastic detritus. This is supported by the occurrence of hydrothermal-derived minerals in the studied samples indicating precipitation temperatures up to 350 °C. Only a dolomitic stromatolite from Strelley Pool shows a superchondritic Y/Ho ratio of 72 and a positive Eu/Eu * anomaly of 1.8, characteristic of chemical precipitates from the Archean seawater. The bulk δ 13C vs. δ 15N values measured in the cherts show a roughly positive co-variation, except for one sample from the North Pole (PI-85-00). The progressive enrichment in 15N and 13C from a pristine source having δ 13C ⩽ -36‰ and δ 15N ⩽ -4‰ is correlated with a progressive depletion in N content and to variations in Ba/La and Co/As ratios. These trends have been interpreted as a progressive hydrothermal alteration of the cherts by metamorphic fluids. Isotopic exchange at 350 °C between NH 4+(rock) and N 2(fluid) may explain the isotopic and elemental composition of N in the studied cherts. However, we need to assume isotopic exchange at 350 °C between carbonate C and graphite to explain the large 13C enrichment recorded. Only sample PI-85-00 shows a large N loss (90%) with a positive δ 15N value (+11‰), while C (up to 120 ppm and δ 13C -38‰) seems to be unaffected. This pattern has been interpreted as the result of devolatilization and alteration (oxidation) of graphite by low-temperature fluids. The 15N- 13C-depleted pristine source has δ 15N values from -7‰ to -4‰ and 40Ar/ 36Ar ratios from 30,000 to 60,000, compatible with an inorganic mantle N source, although the elemental abundance ratios N/C and 40Ar/C are not exactly the same with the mantle source. The component alternatively could be explained by elemental fractionation from metabolic activity of chemolithoautotrophs and methanogens at the proximity to the hydrothermal vents. However, ambiguities between mantle vs organic sources of N subsist and need further experimental work to be fully elucidated.

Effect of sample preparation techniques for carbon and nitrogen stable isotope analysis of hydroxyapatite structures in the form of elasmobranch vertebral centra.

PubMed

Christiansen, Heather M; Hussey, Nigel E; Wintner, Sabine P; Cliff, Geremy; Dudley, Sheldon F J; Fisk, Aaron T

2014-03-15

Bulk stable isotope analysis (SIA) provides an important tool for the study of animal ecology. Elasmobranch vertebral centra can be serially sampled to obtain an isotopic history of an individual over ontogeny. The measured total δ(13)C value, however, may be misinterpreted due to the inclusion of the (13)C-rich inorganic portion. Hydrochloric acid (HCl) is commonly used to remove the inorganic portion of hydroxyapatite structures before undertaking SIA, but more recently ethylenediaminetetraacetic acid (EDTA) has been recommended for elasmobranch vertebrae. These acid treatments may introduce uncertainty on measured δ(13)C and δ(15)N values above instrument precision and the effect of small sample size remains untested for elasmobranch vertebrae. Using a non-dilution program on an isotope ratio mass spectrometer the minimum sample weight of vertebrae required to obtain accurate isotopic values was determined for three shark species: white (Carcharodon carcharias), tiger (Galeocerdo cuvier), and sand tiger (Carcharias taurus). To examine if acid treatment completely removes the inorganic component of the vertebrae or whether the technique introduces its own uncertainty on measured δ(13)C and δ(15)N values, vertebrae samples were analyzed untreated and following EDTA treatment. The minimum sample weight required for accurate stable isotope values and the percentage sample yield following EDTA treatment varied within and among species. After EDTA treatment, white shark vertebrae were all enriched in (13)C and depleted in (15) N, tiger shark vertebrae showed both enrichment and depletion of (13)C and (15)N, and sand tiger shark vertebrae were all depleted in (13)C and (15)N. EDTA treatment of elasmobranch vertebrae produces unpredictable effects (i.e. non-linear and non-correctable) among species in both the percentage sample yield and the measured δ(13)C and δ(15)N values. Prior to initiating a large-scale study, we strongly recommend investigating (i) the minimum weight of vertebral material required to obtain consistent isotopic values and (ii) the effects of EDTA treatment, specific to the study species and the isotope ratio mass spectrometer employed. Copyright © 2014 John Wiley & Sons, Ltd.

Food-web structure of seep sediment macrobenthos from the Gulf of Mexico

NASA Astrophysics Data System (ADS)

Demopoulos, Amanda W. J.; Gualtieri, Daniel; Kovacs, Kaitlin

2010-11-01

The slope environment of the Gulf of Mexico (GOM) supports dense communities of seep megafaunal invertebrates that rely on endosymbiotic bacteria for nutrition. Seep sediments also contain smaller macrofaunal invertebrates whose nutritional pathways are not well understood. Using stable-isotope analysis, we investigate the utilization of chemosynthetically fixed and methane-derived organic matter by macrofauna. Biological sampling was conducted in three lower-slope GOM seep environs: Green Canyon (GC852, 1428 m), Atwater Valley (AT340, 2230 m), and Alaminos Canyon (AC601, 2384 m). Infaunal δ13C and δ15N exhibited a broad range of values; most infauna appeared to be heterotrophic, although several taxa had very light δ15N and δ13C values, indicating possible reliance on chemoautotrophic symbioses. The lightest δ13C and δ15N values were observed in nematodes (δ13C=-54.6±0.1‰, δ15N=-6.1±0.2‰) and one gastropod (δ13C=-54.1‰, δ15N=-1.1‰) from Green Canyon. Mixing-model results indicated that sulfur-oxidizing Beggiatoa may be an important food source for seep infauna; the rate of utilization ranged from 60% to 100% at Green Canyon and Atwater Valley. The overall range in isotope values was similar across the three sites, suggesting that biogeochemical processes may be very similar in these geographically distinct areas.

Stable isotopes reveal the effect of trawl fisheries on the diet of commercially exploited species.

PubMed

Hinz, Hilmar; Moranta, Joan; Balestrini, Stephen; Sciberras, Marija; Pantin, Julia R; Monnington, James; Zalewski, Alex; Kaiser, Michel J; Sköld, Mattias; Jonsson, Patrik; Bastardie, Francois; Hiddink, Jan Geert

2017-07-24

Bottom trawling can change food availability for benthivorous demersal species by (i) changing benthic prey composition through physical seabed impacts and (ii) by removing overall benthic consumer biomass increasing the net availability of benthic prey for remaining individuals. Thus trawling may both negatively and positively influence the quantity and quality of food available. Using δ 13 C and δ 15 N we investigated potential diet changes of three commercially exploited species across trawling gradients in the Kattegat (plaice, dab and Norway lobster (Nephrops)) and the Irish Sea (Nephrops). In the Kattegat, trawling affected primarily the biomass of benthic consumers, lowering competition. Nephrops showed significant positive relationships for δ 13 C and a domed relationship for δ 15 N with trawling. In the Irish Sea, intense trawling had a negative effect on benthic prey. δ 13 C and δ 15 N thus showed the inverse relationships to those observed in the Kattegat. Plaice from the Kattegat, showed a significant relationship with trawling intensity for δ 13 C, but not for δ 15 N. No relationship was found for dab. Changes of δ 13 C and δ 15 N correlated with changes in condition of species. The results show that the removal of demersal competitors and benthos by trawling can change the diets of commercial species, ultimately affecting their body condition.

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

NASA Astrophysics Data System (ADS)

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

2000-04-01

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

A 15 000-year record of climate change in northern New Mexico, USA, inferred from isotopic and elemental contents of bog sediments

USGS Publications Warehouse

Cisneros-Dozal, L. M.; Heikoop, J.M.; Fessenden, J.; Anderson, R. Scott; Meyers, P.A.; Allen, Craig D.; Hess, M.; Larson, T.; Perkins, G.; Rearick, M.

2010-01-01

Elemental (C, N, Pb) and isotopic (δ13C, δ15N) measurements of cored sediment from a small bog in northern New Mexico reveal changes in climate during the Late Pleistocene and Holocene. Abrupt increases in Pb concentration and δ13C values ca. 14 420 cal. YBP indicate significant runoff to the shallow lake that existed at that time. Weathering and transport of local volcanic rocks resulted in the delivery of Pb-bearing minerals to the basin, while a 13C-enriched terrestrial vegetation source increased the δ13C values of the sedimentary material. Wet conditions developed over a 300 a period and lasted for a few hundred years. The Younger Dryas period (ca. 12 700–11 500 cal. YBP) caused a reduction in terrestrial productivity reflected in decreasing C/N values, δ15N values consistently greater than 0‰ and low organic content. By contrast, aquatic productivity increased during the second half of this period, evidenced by increasing δ13C values at the time of highest abundance of algae. Dry conditions ca. 8 000–6 000 cal. YBP were characterised by low organic carbon content and high Pb concentrations, the latter suggesting enhanced erosion and aeolian transport of volcanic rock. The range in δ13C, δ15N and C/N values in the sedimentary record fall within the range of modern plants, except during the periods of runoff and drought. The sedimentary record provides evidence of natural climate variability in northern New Mexico, including short- (multi-centennial) and long-(millennial) term episodes during the Late Pleistocene and Holocene.

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-d 16 and 4-oxo-TEMPO- 15 N,d 16 . 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. Copyright © 2016 John Wiley & Sons, Ltd.

Cluster Roots of Leucadendron laureolum (Proteaceae) and Lupinus albus (Fabaceae) Take Up Glycine Intact: An Adaptive Strategy to Low Mineral Nitrogen in Soils?

PubMed Central

HAWKINS, HEIDI-JAYNE; WOLF, GABRIELLE; STOCK, WILLIAM DAVID

2005-01-01

• Background and Aims South African soils are not only low in phosphorus (P) but most nitrogen (N) is in organic form, and soil amino acid concentrations can reach 2·6 g kg−1 soil. The Proteaceae (a main component of the South African Fynbos vegetation) and some Fabaceae produce cluster roots in response to low soil phosphorus. The ability of these roots to acquire the amino acid glycine (Gly) was assessed. • Methods Uptake of organic N as 13C–15N-Gly was determined in cluster roots and non-cluster roots of Leucadendron laureolum (Proteaceae) and Lupinus albus (Fabaceae) in hydroponic culture, taking account of respiratory loss of 13CO2. • Key Results Both plant species acquired doubly labelled (intact) Gly, and respiratory losses of 13CO2 were small. Lupin (but not leucadendron) acquired more intact Gly when cluster roots were supplied with 13C–15N-Gly than when non-cluster roots were supplied. After treatment with labelled Gly (13C : 15N ratio = 1), lupin cluster roots had a 13C : 15N ratio of about 0·85 compared with 0·59 in labelled non-cluster roots. Rates of uptake of label from Gly did not differ between cluster and non-cluster roots of either species. The ratio of C : N and 13C : 15N in the plant increased in the order: labelled roots < rest of the root < shoot in both species, owing to an increasing proportion of 13C translocation. • Conclusions Cluster roots of lupin specifically acquired more intact Gly than non-cluster roots, whereas Gly uptake by the cluster and non-cluster roots of leucadendron was comparable. The uptake capacities of cluster roots are discussed in relation to spatial and morphological characteristics in the natural environment. PMID:16223736

Reconstruction of paleostorm history using geochemical proxies in sediment cores from Eastern Lake, Florida

NASA Astrophysics Data System (ADS)

Das, O.; Wang, Y.; Donoghue, J. F.; Coor, J. L.; Kish, S.; Elsner, J.; Hu, X. B.; Niedoroda, A. W.; Ye, M.; Xu, Y.

2009-12-01

Analysis of geochemical proxies of coastal lake sediments provides a useful tool for reconstructing paleostorm history. Such paleostorm records can help constrain models that are used to predict future storm events. In this study, we collected two sediment cores (60 and 103 cm long, respectively) from the center of Eastern Lake located on the Gulf coast of NW Florida. These cores, which are mainly composed of organic-rich mud and organic-poor sand, were sub-sampled at 2-3mm intervals for analyses of their organic carbon and nitrogen concentrations as well as δ13C and δ15N isotopic signatures. Selected samples were submitted for radiocarbon dating in order to establish a chronological framework for the interpretation of the geochemical data. There are significant variations in δ13C, δ15N, C%, N% and C/N with depth. The δ13C and δ15N values vary from -21.8‰ to -26.7‰ and 2.6‰ to 5‰, respectively. The stable isotopic signatures of carbon and nitrogen indicate that the sources of organic matter in sediments include terrestrial C3 type vegetation, marine input from Gulf of Mexico and biological productivity within the lake, such as phytoplankton and zooplankton growing in the lacustrine environment. The δ13C and δ15N values exhibit significant negative excursions by 2‰ in a 30 cm thick sand layer, bounded by a rapid return to the base value. A positive shift in the δ15N record observed in the upper part of the cores likely reflects increased anthropogenic input of N such as sewage or septic tank effluents associated with recent development of areas around the lake for human habitation. Similarly, organic C% and N% range from 5.8 to 0.4 and 0.4 to 0.1, respectively. A prominent negative shift by 2σ relative to the baseline in C% and N% has been observed at approx. 55 to 58 cm depth, consisting of an organic-poor sand layer. This shift in C% and N% can be correlated with the negative shift in the δ13C and δ15N values, indicating a major storm event. Radiocarbon dates will allow establishment of the timing of the event and the interpretation of geochemical data in terms of changes in the lake environment.

Glacial to interglacial surface nutrient variations of Bering Deep Basins recorded by δ13C and δ15N of sedimentary organic matter

NASA Astrophysics Data System (ADS)

Nakatsuka, Takeshi; Watanabe, Kazuki; Handa, Nobuhiko; Matsumoto, Eiji; Wada, Eitaro

1995-12-01

Stable carbon and nitrogen isotopic ratios (δ13C and δ15N) of organic matter were measured in three sediment cores from deep basins of the Bering Sea to investigate past changes in surface nutrient conditions. For surface water reconstructions, hemipelagic layers in the cores were distinguished from turbidite layers (on the basis of their sedimentary structures and 14C ages) and analyzed for isotopic studies. Although δ13C profiles may have been affected by diagenesis, both δ15N and δ13C values showed common positive anomalies during the last deglaciation. We explain these anomalies as reflecting suppressed vertical mixing and low nutrient concentrations in surface waters caused by injection of meltwater from alpine glaciers around the Bering Sea. Appendix tables are available with entire article on microfiche. Order from American Geophysical Union, 2000 Florida Avenue, N.W., Washington , DC 20009. Document P95-003; $2.50. Payment must accompany order.

USE OF δ13C, δ15N AND CARBON TO NITROGEN RATIOS TO EVALUATE THE IMPACT OF SEWAGE DERIVED PARTICULATE ORGANIC MATTER ON THE BENTHIC COMMUNITIES OF THE SOUTHERN CALIFORNIA BIGHT

EPA Science Inventory

We present stable isotope (δ¹³C and δ¹⁵N) measurements of particulate organic matter (POM) sources and benthic organic matter (OM) compartments, and sediment C/N ratios from the coastal area of the southern end of the Southern California Bight (SCB). We use ...

Electromagnetics and Electrothermal Approach to Evaluate Failures in Microelectronic Devices Caused by Electrostatic Discharges: Stochastical Aspects of the Device Reliability.

DTIC Science & Technology

1987-08-01

C C CALL THE ELSV SUBROUTINE TO INVERT THE MATRIX. EPO .1D-09 . CALL ELSV(Z,AUX1,AUX2,tN, DE ,EP) WRITE(93,118) DE 118 FORMAT(5X,’ DE -,1E) C C MULTIPLY...IFCABS(W).LT.EP)GO TO 17 DO 13 I=1,N Y’=A( I,K)/W DO 13 J=1,N 13 AC I,J)=A(I,J)-B(J)*Y DE =O.DO DO.15 J=1,N B(J)0O.DO DO 16 I=1,N 16 B(J)=B(J)+A(I,J...15 DE - DE +C(J)*B(J) RETURN 1. DE -1.DO RETURN -18- IMPLICIT COMPLEX*16 (C) IMPLICIT REAL*8 (A-B,E-H,P-z) C C C THIS PROGRAM GIVES THE POTENTIAL AND THE

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 values. Comparative ??13C and ??15N on-line EA-IRMS data from 14 volunteering laboratories document the usefulness and reliability of acetanilides and ureas as EA-IRMS reference materials.

A surrogate analyte-based liquid chromatography-tandem mass spectrometry method for the determination of endogenous cyclic nucleotides in rat brain.

PubMed

Chen, Jie; Tabatabaei, Ali; Zook, Doug; Wang, Yan; Danks, Anne; Stauber, Kathe

2017-11-30

A robust high-performance liquid chromatography tandem mass spectrometry (LC-MS/MS) assay was developed and qualified for the measurement of cyclic nucleotides (cNTs) in rat brain tissue. Stable isotopically labeled 3',5'-cyclic adenosine- 13 C 5 monophosphate ( 13 C 5 -cAMP) and 3',5'-cyclic guanosine- 13 C, 15 N 2 monophosphate ( 13 C 15 N 2 -cGMP) were used as surrogate analytes to measure endogenous 3',5'-cyclic adenosine monophosphate (cAMP) and 3',5'-cyclic guanosine monophosphate (cGMP). Pre-weighed frozen rat brain samples were rapidly homogenized in 0.4M perchloric acid at a ratio of 1:4 (w/v). Following internal standard addition and dilution, the resulting extracts were analyzed using negative ion mode electrospray ionization LC-MS/MS. The calibration curves for both analytes ranged from 5 to 2000ng/g and showed excellent linearity (r 2 >0.996). Relative surrogate analyte-to-analyte LC-MS/MS responses were determined to correct concentrations derived from the surrogate curves. The intra-run precision (CV%) for 13 C 5 -cAMP and 13 C 15 N 2 -cGMP was below 6.6% and 7.4%, respectively, while the inter-run precision (CV%) was 8.5% and 5.8%, respectively. The intra-run accuracy (Dev%) for 13 C 5 -cAMP and 13 C 15 N 2 -cGMP was <11.9% and 10.3%, respectively, and the inter-run Dev% was <6.8% and 5.5%, respectively. Qualification experiments demonstrated high analyte recoveries, minimal matrix effects and low autosampler carryover. Acceptable frozen storage, freeze/thaw, benchtop, processed sample and autosampler stability were shown in brain sample homogenates as well as post-processed samples. The method was found to be suitable for the analysis of rat brain tissue cAMP and cGMP levels in preclinical biomarker development studies. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

Carbon and Nitrogen Metabolism in Mycorrhizal Networks and Mycoheterotrophic Plants of Tropical Forests: A Stable Isotope Analysis1[W

PubMed Central

Courty, Pierre-Emmanuel; Walder, Florian; Boller, Thomas; Ineichen, Kurt; Wiemken, Andres; Rousteau, Alain; Selosse, Marc-André

2011-01-01

Most achlorophyllous mycoheterotrophic (MH) plants obtain carbon (C) from mycorrhizal networks and indirectly exploit nearby autotrophic plants. We compared overlooked tropical rainforest MH plants associating with arbuscular mycorrhizal fungi (AMF) to well-reported temperate MH plants associating with ectomycorrhizal basidiomycetes. We investigated 13C and 15N abundances of MH plants, green plants, and AMF spores in Caribbean rainforests. Whereas temperate MH plants and fungi have higher δ13C than canopy trees, these organisms displayed similar δ13C values in rainforests, suggesting differences in C exchanges. Although temperate green and MH plants differ in δ15N, they display similar 15N abundances, and likely nitrogen (N) sources, in rainforests. Contrasting with the high N concentrations shared by temperate MH plants and their fungi, rainforest MH plants had lower N concentrations than AMF, suggesting differences in C/N of exchanged nutrients. We provide a framework for isotopic studies on AMF networks and suggest that MH plants in tropical and temperate regions evolved different physiologies to adapt in diverging environments. PMID:21527422

1H, 13C, and 15N backbone assignment and secondary structure of the receptor-binding domain of vascular endothelial growth factor.

PubMed Central

Fairbrother, W. J.; Champe, M. A.; Christinger, H. W.; Keyt, B. A.; Starovasnik, M. A.

1997-01-01

Nearly complete sequence-specific 1H, 13C, and 15N resonance assignments are reported for the backbone atoms of the receptor-binding domain of vascular endothelial growth factor (VEGF), a 23-kDa homodimeric protein that is a major regulator of both normal and pathological angiogenesis. The assignment strategy relied on the use of seven 3D triple-resonance experiments [HN(CO)CA, HNCA, HNCO, (HCA)CONH, HN(COCA)HA, HN(CA)HA, and CBCA-(CO)NH] and a 3D 15N-TOCSY-HSQC experiment recorded on a 0.5 mM (12 mg/mL) sample at 500 MHz, pH 7.0, 45 degrees C. Under these conditions, 15N relaxation data show that the protein has a rotational correlation time of 15.0 ns. Despite this unusually long correlation time, assignments were obtained for 94 of the 99 residues; 8 residues lack amide 1H and 15N assignments, presumably due to rapid exchange of the amide 1H with solvent under the experimental conditions used. The secondary structure of the protein was deduced from the chemical shift indices of the 1H alpha, 13C alpha, 13C beta, and 13CO nuclei, and from analysis of backbone NOEs observed in a 3D 15N-NOESY-HSQC spectrum. Two helices and a significant amount of beta-sheet structure were identified, in general agreement with the secondary structure found in a recently determined crystal structure of a similar VEGF construct [Muller YA et al., 1997, Proc Natl Acad Sci USA 94:7192-7197]. PMID:9336848

Stable isotope ratios of carbon, nitrogen and oxygen in killer whales (Orcinus orca) stranded on the coast of Hokkaido, Japan.

PubMed

Endo, Tetsuya; Kimura, Osamu; Sato, Rie; Kobayashi, Mari; Matsuda, Ayaka; Matsuishi, Takashi; Haraguchi, Koichi

2014-09-15

We analyzed δ(13)C, δ(15)N and δ(18)O in the muscle and liver from killer whales stranded on the coast of Japan. The δ(15)N values in the muscle samples from calves were apparently higher than those in their lactating mothers, suggesting that nursing may result in the higher δ(15)N values in the muscle samples of calves. The δ(15)N value in the muscle samples of male and female whales, except for the calves, were positively correlated with the δ(13)C values and body length, suggesting that the increases in δ(15)N were due to the growth of the whales and increase in their trophic level. In contrast, the δ(18)O values in the muscle samples of female whales except for the calves were negatively correlated with the δ(13)C and δ(15)N values. The δ(18)O may be lower in whales occupying higher trophic positions (δ(15)N), although it might also be affected by geographic and climatic conditions. Copyright © 2014 Elsevier Ltd. All rights reserved.

Wild rabbit host and some parasites show trophic-level relationships for delta 13C and delta 15N: a first report.

PubMed

Boag, B; Neilson, R; Robinson, D; Scrimgeour, C M; Handley, L L

1998-01-01

We report the first isotopic study of an animal host-parasite system. Parasitic, intestinal nematodes, Graphidium strigosum and Passalurus ambiguus, were 15N-enriched relative to their host, the European rabbit Oryctolagus cuniculus, while parasitic cestodes, Cittataenia denticulata and Mosgovoyia pectinata, were 15N-depleted, suggesting different trophic relationships. Host embryos were more similar in their delta 13C and delta 15N values to maternal muscle than were any of the parasites. Coprophagy, the direct recycling of food by the rabbit eating its own faeces, did not lead to isotopic differences between stomach contents and faeces, suggesting that the major point for isotopic discrimination in lagomorph nitrogen metabolism is in the animal rather than in the gut. We conclude that bulk delta 13C and delta 15N can reveal valuable new information about host-parasite relationships, and these could be explored further at the biochemical level using compound-specific isotopic analyses.

Dietary response of sympatric deer to fire using stable isotope analysis of liver tissue

USGS Publications Warehouse

Walter, W. David; Zimmerman, T.J.; Leslie, David M.; Jenks, J.A.

2009-01-01

Carbon (??13C) and nitrogen (??15N) isotopes in biological samples from large herbivores identify photosynthetic pathways (C3 vs. C4) of plants they consumed and can elucidate potential nutritional characteristics of dietary selection. Because large herbivores consume a diversity of forage types, ??13C and ??15N in their tissue can index ingested and assimilated diets through time. We assessed ??13C and ??15N in metabolically active liver tissue of sympatric mule deer (Odocoileus hemionus) and white-tailed deer (O. virginianus) to identify dietary disparity resulting from use of burned and unburned areas in a largely forested landscape. Interspecific variation in dietary disparity of deer was documented 2-3 years post-fire in response to lag-time effects of vegetative response to burning and seasonal (i.e., summer, winter) differences in forage type. Liver ??13C for mule deer were lower during winter and higher during summer 2 years post-fire on burned habitat compared to unburned habitat suggesting different forages were consumed by mule deer in response to fire. Liver ??15N for both species were higher on burned than unburned habitat during winter and summer suggesting deer consumed more nutritious forage on burned habitat during both seasons 2 and 3 years post-fire. Unlike traditional methods of dietary assessment that do not measure uptake of carbon and nitrogen from dietary components, analyses of stable isotopes in liver or similar tissue elucidated ??13C and ??15N assimilation from seasonal dietary components and resulting differences in the foraging ecology of sympatric species in response to fire.

Biogeochemical tracers of the marine cyanobacterium Trichodesmium

NASA Astrophysics Data System (ADS)

Carpenter, Edward J.; Harvey, H. Rodger; Fry, Brian; Capone, Douglas G.

1997-01-01

We examined the utility of several biogeochemical tracers for following the fate of the planktonic diazotrophic cyanobacterium Trichodesmium in the sea. The presence of a (CIO) fatty acid previously reported was observed in a culture of Trichodesmium but was not found in natural samples. This cyanobacterium had high concentrations of C 14 and C 16 acids, with lesser amounts of several saturated and unsaturated C 18 fatty acids. This composition was similar to that of other marine cyanobacteria. The major hydrocarbon identified was the C 17n-alkane, which was present in all samples from the five stations examined. Sterols common to algae and copepods were observed in many samples along with hopanoids representative of bacteria, suggesting a varied community structure in colonies collected from different stations. We found no unique taxonomic marker of Trichodesmium among the sterols. Measurements of the σ 15N and σ 13C in Trichodesmium samples from the SW Sargasso and NW Caribbean Seas averaged -0.4960 (range from -0.7 to -0.25960) and -12.9%0 (range from -15.2 to -11.9960), respectively, thus confirming previous observations that this cyanobacterial diazotroph has both the lowest σ 15N and highest σ 13C of any marine phytoplankter observed to date. A culture of Trichodesmium grown under diazotrophic conditions had a σ 15N between -1.3 and -3.6960. Our results support the supposition that the relatively low σ 15N and high σ 13C values observed in suspended and sediment-trapped material from some tropical and subtropical seas result from substantial input of C and N by Trichodesmium.

Nitrogen cycling following The Great Oxidation Event, evidence from the Paleoproterozoic of Fennoscandia.

NASA Astrophysics Data System (ADS)

Junium, C. K.; Kump, L.; Arthur, M. A.; Melezhik, V.; Lepland, A.; Members of the FAR-DEEP Drilling Team

2011-12-01

The Fennoscandia Arctic Russia - Drilling Early Earth Project (FAR-DEEP) recovered core materials spanning the early Paleoproterozoic of Arctic Russia under the auspices of the International Continental Scientific Drilling Program. Here we present N and C isotopic data documenting N and C cycle dynamics during this critical interval of Earth history. Additionally, we will discuss the challenges of nitrogen isotope studies in such ancient sediments and the methods that we have utilized to test the fidelity of our nitrogen isotope data. Nitrogen isotope studies in very ancient sedimentary rocks, like those recovered by the FAR-DEEP are plagued by the concerns of diagenetic and metamorphic overprinting. Nitrogen is often present in very low concentrations and in a variety of inorganic phases that may or may not be derived from the ambient organic matter. For these reasons, bulk sediment δ15N data can be at best, ambiguous. To overcome these issues we have utilized kerogens for δ15N and δ13C analyses. The large difference between bulk and kerogen δ15N data demonstrates that inorganic N is anomalously 15N-enriched, by up to 7% and bulk δ15N values substantially overestimate the magnitude of the 15N variability in the Onega Basin (OB) sediments. Metasomatic processes during basinal magamatic activity resulted in the addition of 15N-enriched inorganic-N. Authigenic K-bearing micas are common in intervals where bulk δ15N values are 15N-enriched, suggesting that secondary mineral phases have retained 15N-enriched ammonia generated during metsomatism. The FAR-DEEP drilling team has documented an anomalously large, and rapid δ13C shift of -17% in carbonates and organic matter of the Zhaoneskaya Formation (ZF) of the OB following the extended period of 13Ccarb-enrichment know as the Lomagundi-Jatuli event. The isotopic shift in reduced carbon has also been recognized in the Franceville Formation of Gabon, termed here as "Shunga-Francevillian" anomaly, and may reflect the global oxidation of organic matter buried during the buildup of atmospheric oxygen in response to Lomagundi-Jatuli carbon burial. The dynamic response of the nitrogen cycle in the ZF is consistent with increased availability of O2 in the water column and is similar to the response documented in Archean sequences. Kerogen δ15N values are below 2%, most likely reflecting a biological N2-fixation source for nutrient-nitrogen with little influence from denitrification. δ13C values increase from -26% to -19% signaling a transient increase in the burial of organic carbon and net production of O2. Transition from a largely anoxic OB water column to one that was oxidized in its surface waters would have allowed for redox cycling of nitrogen and accompanying 15N-enrichment. Thus, the observed δ15N increase of 5% reflects an expansion in denitrification and associated reactions and oxidation of the OB water column under elevated atmospheric O2. At the end of the precipitous decrease in δ13C values δ15N values return pre-excursion values of ~+2%. This drop in δ13C and δ15N suggests a return to less oxidizing conditions in the OB following drawdown of atmospheric O2 during organic matter oxidation.

Nitrogen Fractionation in Protoplanetary Disks from the H13CN/HC15N Ratio

NASA Astrophysics Data System (ADS)

Guzmán, V. V.; Öberg, K. I.; Huang, J.; Loomis, R.; Qi, C.

2017-02-01

Nitrogen fractionation is commonly used to assess the thermal history of solar system volatiles. With ALMA it is for the first time possible to directly measure {}14{{N}}/{}15{{N}} ratios in common molecules during the assembly of planetary systems. We present ALMA observations of the {{{H}}}13{CN} and {{HC}}15{{N}} J=3-2 lines at 0.″5 angular resolution, toward a sample of six protoplanetary disks, selected to span a range of stellar and disk structure properties. Adopting a typical {}12{{C}}/{}13{{C}} ratio of 70, we find comet-like {}14{{N}}/{}15{{N}} ratios of 80-160 in five of the disks (3 T Tauri and 2 Herbig Ae disks) and lack constraints for one of the T Tauri disks (IM Lup). There are no systematic differences between T Tauri and Herbig Ae disks, or between full and transition disks within the sample. In addition, no correlation is observed between disk-averaged D/H and {}14{{N}}/{}15{{N}} ratios in the sample. One of the disks, V4046 Sgr, presents unusually bright HCN isotopologue emission, enabling us to model the radial profiles of {{{H}}}13{CN} and {{HC}}15{{N}}. We find tentative evidence of an increasing {}14{{N}}/{}15{{N}} ratio with radius, indicating that selective photodissociation in the inner disk is important in setting the {}14{{N}}/{}15{{N}} ratio during planet formation.

Quantifying MTBE biodegradation in the Vandenberg Air Force Base ethanol release study using stable carbon isotopes

NASA Astrophysics Data System (ADS)

McKelvie, Jennifer R.; Mackay, Douglas M.; de Sieyes, Nicholas R.; Lacrampe-Couloume, Georges; Sherwood Lollar, Barbara

2007-12-01

Compound-specific isotope analysis (CSIA) was used to assess biodegradation of MTBE and TBA during an ethanol release study at Vandenberg Air Force Base. Two continuous side-by-side field releases were conducted within a preexisting MTBE plume to form two lanes. The first involved the continuous injection of site groundwater amended with benzene, toluene and o-xylene ("No ethanol lane"), while the other involved the continuous injection of site groundwater amended with benzene, toluene and o-xylene and ethanol ("With ethanol lane"). The δ 13C of MTBE for all wells in the "No ethanol lane" remained constant during the experiment with a mean value of - 31.3 ± 0.5‰ ( n = 40), suggesting the absence of any substantial MTBE biodegradation in this lane. In contrast, substantial enrichment in 13C of MTBE by 40.6‰, was measured in the "With ethanol lane", consistent with the effects of biodegradation. A substantial amount of TBA (up to 1200 μg/L) was produced by the biodegradation of MTBE in the "With ethanol lane". The mean value of δ 13C for TBA in groundwater samples in the "With ethanol lane" was - 26.0 ± 1.0‰ ( n = 32). Uniform δ 13C TBA values through space and time in this lane suggest that substantial anaerobic biodegradation of TBA did not occur during the experiment. Using the reported range in isotopic enrichment factors for MTBE of - 9.2‰ to - 15.6‰, and values of δ 13C of MTBE in groundwater samples, MTBE first-order biodegradation rates in the "With ethanol lane" were 12.0 to 20.3 year - 1 ( n = 18). The isotope-derived rate constants are in good agreement with the previously published rate constant of 16.8 year - 1 calculated using contaminant mass-discharge for the "With ethanol lane".

Food-web structure of seep sediment macrobenthos from the Gulf of Mexico

USGS Publications Warehouse

Demopoulos, Amanda W.J.; Gualtieri, Daniel; Kovacs, Kaitlin

2010-01-01

The slope environment of the Gulf of Mexico (GOM) supports dense communities of seep megafaunal invertebrates that rely on endosymbiotic bacteria for nutrition. Seep sediments also contain smaller macrofaunal invertebrates whose nutritional pathways are not well understood. Using stable-isotope analysis, we investigate the utilization of chemosynthetically fixed and methane-derived organic matter by macrofauna. Biological sampling was conducted in three lower-slope GOM seep environs: Green Canyon (GC852, 1428 m), Atwater Valley (AT340, 2230 m), and Alaminos Canyon (AC601, 2384 m). Infaunal delta13C and delta15N exhibited a broad range of values; most infauna appeared to be heterotrophic, although several taxa had very light delta15N and delta13C values, indicating possible reliance on chemoautotrophic symbioses. The lightest delta13C and delta15N values were observed in nematodes (delta13C=-54.6 + or - 0.1 per mil, delta15N=-6.1 + or - 0.2 per mil) and one gastropod (delta13C=-54.1 per mil, delta15N=-1.1 per mil) from Green Canyon. Mixing-model results indicated that sulfur-oxidizing Beggiatoa may be an important food source for seep infauna; the rate of utilization ranged from 60% to 100% at Green Canyon and Atwater Valley. The overall range in isotope values was similar across the three sites, suggesting that biogeochemical processes may be very similar in these geographically distinct areas.

Variability in the preservation of the isotopic composition of collagen from fossil bone

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

Tuross, N.; Fogel, M.L.; Hare, P.E.

1988-04-01

Collagen from bone was prepared by several methods. For modern and well-preserved bone the {delta}{sup 13}C and {delta}{sup 15}N of collagen replicas obtained after HCl or EDTA demineralization were similar to those obtained with a gelatinization procedure. However, in more poorly preserved fossil bone the {delta}{sup 13}C and {delta}{sup 15}N varied among the different protein extracts. The yield of collagen obtained with EDTA demineralization was consistently higher than extraction procedures that used HCl. The {delta}{sup 13}C of individual amino acids separated from the collagen of modern and fossil whale bone varied up to 17{per thousand}, and the {delta}{sup 15}N frommore » the same amino acids ranged over 47{per thousand}. The {delta}{sup 13}C and {delta}{sup 15}N of most amino acids clustered closely to the average of the HCl insoluble collagen. The {delta}{sup 13}C of the major amino acid in collagen, glycine, differed from the average HCl insoluble collagen by approximately 8{per thousand} in the fossil whale and 14{per thousand} in the modern whale. The {delta}{sup 15}N of glycine differed from the average HCl insoluble values by approximately 4{per thousand} in the fossil whale and 7{per thousand} in the modern whale. Thus, diagenetic changes that alter the ratio of glycine to other amino acids in bone can be expected to perturb the values for carbon and nitrogen isotopes.« less

Dual element ((15)N/(14)N, (13)C/(12)C) isotope analysis of glyphosate and AMPA by derivatization-gas chromatography isotope ratio mass spectrometry (GC/IRMS) combined with LC/IRMS.

PubMed

Mogusu, Emmanuel O; Wolbert, J Benjamin; Kujawinski, Dorothea M; Jochmann, Maik A; Elsner, Martin

2015-07-01

To assess sources and degradation of the herbicide glyphosate [N-(phosphonomethyl) glycine] and its metabolite AMPA (aminomethylphosphonic acid), concentration measurements are often inconclusive and even (13)C/(12)C analysis alone may give limited information. To advance isotope ratio analysis of an additional element, we present compound-specific (15)N/(14)N analysis of glyphosate and AMPA by a two step derivatization in combination with gas chromatography/isotope ratio mass spectrometry (GC/IRMS). The N-H group was derivatized with isopropyl chloroformate (iso-PCF), and remaining acidic groups were subsequently methylated with trimethylsilyldiazomethane (TMSD). Iso-PCF treatment at pH <10 gave too low (15)N/(14)N ratios indicating an incomplete derivatization; in contrast, too high (15)N/(14)N ratios at pH >10 indicated decomposition of the derivative. At pH 10, and with an excess of iso-PCF by 10-24, greatest yields and accurate (15)N/(14)N ratios were obtained (deviation from elemental analyzer-IRMS: -0.2 ± 0.9% for glyphosate; -0.4 ± 0.7% for AMPA). Limits for accurate δ(15)N analysis of glyphosate and AMPA were 150 and 250 ng injected, respectively. A combination of δ(15)N and δ(13)C analysis by liquid chromatography/isotope ratio mass spectrometry (LC/IRMS) (1) enabled an improved distinction of commercial glyphosate products and (2) showed that glyphosate isotope values during degradation by MnO2 clearly fell outside the commercial product range. This highlights the potential of combined carbon and nitrogen isotopes analysis to trace sources and degradation of glyphosate.

Progress in proton-detected solid-state NMR (SSNMR): Super-fast 2D SSNMR collection for nano-mole-scale proteins

NASA Astrophysics Data System (ADS)

Ishii, Yoshitaka; Wickramasinghe, Ayesha; Matsuda, Isamu; Endo, Yuki; Ishii, Yuji; Nishiyama, Yusuke; Nemoto, Takahiro; Kamihara, Takayuki

2018-01-01

Proton-detected solid-state NMR (SSNMR) spectroscopy has attracted much attention due to its excellent sensitivity and effectiveness in the analysis of trace amounts of amyloid proteins and other important biological systems. In this perspective article, we present the recent sensitivity limit of 1H-detected SSNMR using "ultra-fast" magic-angle spinning (MAS) at a spinning rate (νR) of 80-100 kHz. It was demonstrated that the high sensitivity of 1H-detected SSNMR at νR of 100 kHz and fast recycling using the paramagnetic-assisted condensed data collection (PACC) approach permitted "super-fast" collection of 1H-detected 2D protein SSNMR. A 1H-detected 2D 1H-15N correlation SSNMR spectrum for ∼27 nmol of a uniformly 13C- and 15N-labeled GB1 protein sample in microcrystalline form was acquired in only 9 s with 50% non-uniform sampling and short recycle delays of 100 ms. Additional data suggests that it is now feasible to detect as little as 1 nmol of the protein in 5.9 h by 1H-detected 2D 1H-15N SSNMR at a nominal signal-to-noise ratio of five. The demonstrated sensitivity is comparable to that of modern solution protein NMR. Moreover, this article summarizes the influence of ultra-fast MAS and 1H-detection on the spectral resolution and sensitivity of protein SSNMR. Recent progress in signal assignment and structural elucidation by 1H-detected protein SSNMR is outlined with both theoretical and experimental aspects.

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 populations in terms of isotopic composition, and probably ecology.

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

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

Chace, D.H.

1989-01-01

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

Quantifying the effect of plant growth on litter decomposition using a novel, triple-isotope label approach

NASA Astrophysics Data System (ADS)

Ernakovich, J. G.; Baldock, J.; Carter, T.; Davis, R. A.; Kalbitz, K.; Sanderman, J.; Farrell, M.

2017-12-01

Microbial degradation of plant detritus is now accepted as a major stabilizing process of organic matter in soils. Most of our understanding of the dynamics of decomposition come from laboratory litter decay studies in the absence of plants, despite the fact that litter decays in the presence of plants in many native and managed systems. There is growing evidence that living plants significantly impact the degradation and stabilization of litter carbon (C) due to changes in the chemical and physical nature of soils in the rhizosphere. For example, mechanistic studies have observed stimulatory effects of root exudates on litter decomposition, and greenhouse studies have shown that living plants accelerate detrital decay. Despite this, we lack a quantitative understanding of the contribution of living plants to litter decomposition and how interactions of these two sources of C build soil organic matter (SOM). We used a novel triple-isotope approach to determine the effect of living plants on litter decomposition and C cycling. In the first stage of the experiment, we grew a temperate grass commonly used for forage, Poa labillardieri, in a continuously-labelled atmosphere of 14CO2 fertilized with K15NO3, such that the grass biomass was uniformly labelled with 14C and 15N. In the second stage, we constructed litter decomposition mescososms with and without a living plant to test for the effect of a growing plant on litter decomposition. The 14C/15N litter was decomposed in a sandy clay loam while a temperate forage grass, Lolium perenne, grew in an atmosphere of enriched 13CO2. The fate of the litter-14C/15N and plant-13C was traced into soil mineral fractions and dissolved organic matter (DOM) over the course of nine weeks using four destructive harvests of the mesocosms. Our preliminary results suggest that living plants play a major role in the degradation of plant litter, as litter decomposition was greater, both in rate and absolute amount, for soil mesocosms with a growing plant. Our observations during the decomposition experiment suggests that plant roots physically disrupted litter to increase decomposition. Isotopic analyses are currently underway, and transformations of litter-14C will be presented. Refining our understanding of in situ litter decay will add to our growing knowledge of the C cycle.

Isotopic ratios in outbursting comet C/2015 ER61

NASA Astrophysics Data System (ADS)

Yang, Bin; Hutsemékers, Damien; Shinnaka, Yoshiharu; Opitom, Cyrielle; Manfroid, Jean; Jehin, Emmanuël; Meech, Karen J.; Hainaut, Olivier R.; Keane, Jacqueline V.; Gillon, Michaël

2018-02-01

Isotopic ratios in comets are critical to understanding the origin of cometary material and the physical and chemical conditions in the early solar nebula. Comet C/2015 ER61 (PANSTARRS) underwent an outburst with a total brightness increase of 2 magnitudes on the night of 2017 April 4. The sharp increase in brightness offered a rare opportunity to measure the isotopic ratios of the light elements in the coma of this comet. We obtained two high-resolution spectra of C/2015 ER61 with UVES/VLT on the nights of 2017 April 13 and 17. At the time of our observations, the comet was fading gradually following the outburst. We measured the nitrogen and carbon isotopic ratios from the CN violet (0, 0) band and found that 12C/13C = 100 ± 15, 14N/15N = 130 ± 15. In addition, we determined the 14N/15N ratio from four pairs of NH2 isotopolog lines and measured 14N/15N = 140 ± 28. The measured isotopic ratios of C/2015 ER61 do not deviate significantly from those of other comets.

Retrospective characterization of ontogenetic shifts in killer whale diets via δ13C and δ15N analysis of teeth

USGS Publications Warehouse

Newsome, Seth D.; Etnier, Michael A.; Monson, Daniel H.; Fogel, Marilyn L.

2009-01-01

Metabolically inert, accretionary structures such as the dentin growth layers in teeth provide a life history record of individual diet with near-annual resolution. We constructed ontogenetic ??13C and ??15N profiles by analyzing tooth dentin growth layers from 13 individual killer whales Orcinus orca collected in the eastern northeast Pacific Ocean between 1961 and 2003. The individuals sampled were 6 to 52 yr old, representing 2 ecotypes-resident and transient - collected across ???25?? of latitude. The average isotopic values of transient individuals (n = 10) are consistent with a reliance on mammalian prey, while the average isotopic values of residents (n = 3) are consistent with piscivory. Regardless of ecotype, most individuals show a decrease in ??15N values of ???2.5% through the first 3 yr of life, roughly equivalent to a decrease of one trophic level. We interpret this as evidence of gradual weaning, after which, ontogenetic shifts in isotopic values are highly variable. A few individuals (n = 2) maintained relatively stable ??15N and ??13C values throughout the remainder of their lives, whereas ??15N values of most (n = 11) increased by ???1.5%, suggestive of an ontogenetic increase in trophic level. Significant differences in mean ??13C and ??15N values among transients collected off California suggest that individuality in prey preferences may be prevalent within this ecotype. Our approach provides retrospective individual life history and dietary information that cannot be obtained through traditional field observations of free-ranging and elusive species such as killer whales, including unique historic ecological information that pre-dates modern studies. By providing insights into individual diet composition, stable isotope analysis of teeth and/or bones may be the only means of evaluating a number of hypothesized historical dietary shifts in killer whales of the northeast Pacific Ocean. ?? Inter-Research 2009.

Retrospective characterization of ontogenetic shifts in killer whale diets via δ13C and δ15N analysis of teeth

USGS Publications Warehouse

Newsome, Seth D.; Etnier, Michael A.; Monson, Daniel H.; Fogel, Marilyn L.

2009-01-01

Metabolically inert, accretionary structures such as the dentin growth layers in teeth provide a life history record of individual diet with near-annual resolution. We constructed ontogenetic δ13C and δ15N profiles by analyzing tooth dentin growth layers from 13 individual killer whales Orcinus orca collected in the eastern northeast Pacific Ocean between 1961 and 2003. The individuals sampled were 6 to 52 yr old, representing 2 ecotypes—resident and transient—collected across ~25° of latitude. The average isotopic values of transient individuals (n = 10) are consistent with a reliance on mammalian prey, while the average isotopic values of residents (n = 3) are consistent with piscivory. Regardless of ecotype, most individuals show a decrease in δ15N values of ~2.5‰ through the first 3 yr of life, roughly equivalent to a decrease of one trophic level. We interpret this as evidence of gradual weaning, after which, ontogenetic shifts in isotopic values are highly variable. A few individuals (n = 2) maintained relatively stable δ15N and δ13C values throughout the remainder of their lives, whereas δ15N values of most (n = 11) increased by ~1.5‰, suggestive of an ontogenetic increase in trophic level. Significant differences in mean δ13C and δ15N values among transients collected off California suggest that individuality in prey preferences may be prevalent within this ecotype. Our approach provides retrospective individual life history and dietary information that cannot be obtained through traditional field observations of free-ranging and elusive species such as killer whales, including unique historic ecological information that pre-dates modern studies. By providing insights into individual diet composition, stable isotope analysis of teeth and/or bones may be the only means of evaluating a number of hypothesized historical dietary shifts in killer whales of the northeast Pacific Ocean

Stellar Origin of 15N-rich Presolar SiC Grains of Type AB: Supernovae with Explosive Hydrogen Burning

NASA Astrophysics Data System (ADS)

Liu, Nan; Nittler, Larry R.; Pignatari, Marco; O'D. Alexander, Conel M.; Wang, Jianhua

2017-06-01

We report C, N, and Si isotopic data for 59 highly 13C-enriched presolar submicron- to micron-sized SiC grains from the Murchison meteorite, including eight putative nova grains (PNGs) and 29 15N-rich (14N/15N ≤ solar) AB grains, and their Mg-Al, S, and Ca-Ti isotope data when available. These 37 grains are enriched in 13C, 15N, and 26Al with the PNGs showing more extreme enhancements. The 15N-rich AB grains show systematically higher 26Al and 30Si excesses than the 14N-rich AB grains. Thus, we propose to divide the AB grains into groups 1 (14N/15N < solar) and 2 (14N/15N ≥ solar). For the first time, we have obtained both S and Ti isotopic data for five AB1 grains and one PNG and found 32S and/or 50Ti enhancements. Interestingly, one AB1 grain had the largest 32S and 50Ti excesses, strongly suggesting a neutron-capture nucleosynthetic origin of the 32S excess and thus the initial presence of radiogenic 32Si (t 1/2 = 153 years). More importantly, we found that the 15N and 26Al excesses of AB1 grains form a trend that extends to the region in the N-Al isotope plot occupied by C2 grains, strongly indicating a common stellar origin for both AB1 and C2 grains. Comparison of supernova models with the AB1 and C2 grain data indicates that these grains came from supernovae that experienced H ingestion into the He/C zones of their progenitors.

Evaluating sourcing and fluvial integration of plant wax biomarkers from the Peruvian Andes to Amazonian lowlands

NASA Astrophysics Data System (ADS)

Wu, M. S.; Feakins, S. J.; Ponton, C.; West, A. J.; Galy, V.

2017-12-01

The carbon and hydrogen isotopic compositions (respectively δ13C and δD) of plant wax biomarkers have been widely used to reconstruct past climate and environment. To understand how leaf waxes are sourced within a river catchment, and how their isotopic signature is transferred from source to sink, we study δ13C and δD of C29 n-alkanes and C30 n-alkanoic acids in the Madre de Dios River catchment along the eastern flank of the Peruvian Andes. We sampled soils across a 3.5km elevation transect and find gradients in δ13Cwax (ca. +1.5‰/km) and δDwax (ca. -10 ‰/km) similar to gradients in tree canopy leaves (Feakins et al., 2016 GCA; Wu et al., 2017 GCA). We also collected river suspended sediment samples along the Madre de Dios River and its tributaries, which together drain an area of 75,400 km2 and 6 km of elevation. We utilize soil data and a digital elevation model to construct isoscapes, delineate catchments for each river sampling location, predict river values assuming spatial uniform integration, and compare our predictions with observed values. Although both compounds generally follow isotopic gradients defined by catchment elevations, the dual isotope and compound-class comparison reveals additional processes. For C30 n-alkanoic acid we find an up to 1km lower-than-expected catchment signal, indicating degradation of upland contributions in transit and replacement with lowland inputs. In contrast, mountain-front river locations are susceptible to upland-biases (up to 1km higher sourcing) in C29 n-alkane sourcing, likely due to enhanced erosion and higher leaf wax stock in Andean soil compared to the lowland, and greater persistence of n-alkanes than n-alkanoic acids. For both compounds, the bias is eliminated with several hundred km of river transit across the floodplain. In one location, we identify significant petrogenic contamination of n-alkanes but not n-alkanoic acids. These results indicate the power in combining dual compound classes and dual isotopes to analyze source-to-sink processes and to evaluate sourcing of river exported plant wax biomarkers.

Effects of acidification, lipid removal and mathematical normalization on carbon and nitrogen stable isotope compositions in beaked whale (Ziphiidae) bone.

PubMed

Tatsch, Ana Carolina C; Secchi, Eduardo R; Botta, Silvina

2016-02-15

The analysis of stable isotopes in tissues such as teeth and bones has been used to study long-term trophic ecology and habitat use in marine mammals. However, carbon isotope ratios (δ(13) C values) can be altered by the presence of (12) C-rich lipids and carbonates. Lipid extraction and acidification are common treatments used to remove these compounds. The impact of lipids and carbonates on carbon and nitrogen isotope ratios (δ(15) N values), however, varies among tissues and/or species, requiring taxon-specific protocols to be developed. The effects of lipid extraction and acidification and their interaction on carbon and nitrogen isotope values were studied for beaked whale (Ziphiidae) bone samples. δ(13) C and δ(15) N values were determined in quadruplicate samples: control, lipid-extracted, acidified and lipid-extracted followed by acidification. Samples were analyzed by means of elemental analysis isotope ratio mass spectrometry. Furthermore, the efficiency of five mathematical models developed for estimating lipid-normalized δ(13) C values from untreated δ(13) C values was tested. Significant increases in δ(13) C values were observed after lipid extraction. No significant changes in δ(13) C values were found in acidified samples. An interaction between both treatments was demonstrated for δ(13) C but not for δ(15) N values. No change was observed in δ(15) N values for lipid-extracted and/or acidified samples. Although all tested models presented good predictive power to estimate lipid-free δ(13) C values, linear models performed best. Given the observed changes in δ(13) C values after lipid extraction, we recommend a priori lipid extraction or a posteriori lipid normalization, through simple linear models, for beaked whale bones. Furthermore, acidification seems to be an unnecessary step before stable isotope analysis, at least for bone samples of ziphiids. Copyright © 2015 John Wiley & Sons, Ltd. Copyright © 2015 John Wiley & Sons, Ltd.

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 used in practice.

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. PMID:24205126

Calcification rate and the stable carbon, oxygen, and nitrogen isotopes in the skeleton, host tissue, and zooxanthellae of bleached and recovering Hawaiian corals

NASA Astrophysics Data System (ADS)

Rodrigues, Lisa J.; Grottoli, Andréa G.

2006-06-01

We tested the effectiveness of stable isotopes as recorders of physiological changes that occur during coral bleaching and recovery. Montipora capitata and Porites compressa fragments were bleached in outdoor tanks with seawater temperature raised to 30 °C (treatment corals) for one month. Additional fragments were maintained at 27 °C in separate tanks (control corals). After one month, (0 months recovery), buoyant weight was measured and a subset of fragments was frozen. Remaining fragments were returned to the reef for recovery. After 1.5, 4, and 8 months, fragments were collected, measured for buoyant weight, and frozen. Fragments were analyzed for stable carbon and oxygen isotopic compositions of the skeleton (δ 13C s; δ 18O s) and nitrogen and carbon isotopic compositions of the host tissue (δ 15N h; δ 13C h) and zooxanthellae (δ 15N z; δ 13C z). δ 13C s decreased immediately after bleaching in M. capitata, but not in P. compressa. δ 18O s of both species failed to record the warming event. During the remaining months of recovery, δ 13C s and δ 18O s were more enriched in treatment than control corals due to decreases in calcification and metabolic fractionation during that time. Increased δ 15N h of treatment P. compressa may be due to expelled zooxanthellae during bleaching and recovery. Increased δ 15N z at 1.5 months in treatment fragments of both species reflects the increased incorporation of dissolved inorganic nitrogen to facilitate mitotic cell division and/or chl a/cell recovery. Changes in δ 13C h and δ 13C z at 1.5 months in treatment M. capitata indicated a large increase in heterotrophically acquired carbon relative to photosynthetically fixed carbon. We experimentally show that isotopes in coral skeleton, host tissue and zooxanthellae can be used to verify physiological changes during bleaching and recovery, but their use as a proxy for past bleaching events in the skeletal record is limited.

Alteration of the Carbon and Nitrogen Isotopic Composition in the Martian Surface Rocks Due to Cosmic Ray Exposure

NASA Technical Reports Server (NTRS)

Pavlov, A. A.; Pavlov, A. K.; Ostryakov, V. M.; Vasilyev, G. I.; Mahaffy, P.; Steele, A.

2014-01-01

C-13/C-12 and N-15/N-14 isotopic ratios are pivotal for our understanding of the Martian carbon cycle, history of the Martian atmospheric escape, and origin of the organic compounds on Mars. Here we demonstrate that the carbon and nitrogen isotopic composition of the surface rocks on Mars can be significantly altered by the continuous exposure of Martian surface to cosmic rays. Cosmic rays can effectively produce C-13 and N-15 isotopes via spallation nuclear reactions on oxygen atoms in various Martian rocks. We calculate that in the top meter of the Martian rocks, the rates of production of both C-13 and N-15 due to galactic cosmic rays (GCRs) exposure can vary within 1.5-6 atoms/cm3/s depending on rocks' depth and chemical composition. We also find that the average solar cosmic rays can produce carbon and nitrogen isotopes at a rate comparable to GCRs in the top 5-10 cm of the Martian rocks. We demonstrate that if the total carbon content in a surface Martian rock is <10 ppm, then the "light," potentially "biological" C-13/C-12 ratio would be effectively erased by cosmic rays over 3.5 billion years of exposure. We found that for the rocks with relatively short exposure ages (e.g., 100 million years), cosmogenic changes in N-15/N-14 ratio are still very significant. We also show that a short exposure to cosmic rays of Allan Hills 84001 while on Mars can explain its high-temperature heavy nitrogen isotopic composition (N-15/N-14). Applications to Martian meteorites and the current Mars Science Laboratory mission are discussed.

Seasonal variation in natural abundance of δ13C and 15N in Salicornia brachiata Roxb. populations from a coastal area of India.

PubMed

Chaudhary, Doongar R; Seo, Juyoung; Kang, Hojeong; Rathore, Aditya P; Jha, Bhavanath

2018-05-01

High and fluctuating salinity is characteristic for coastal salt marshes, which strongly affect the physiology of halophytes consequently resulting in changes in stable isotope distribution. The natural abundance of stable isotopes (δ 13 C and δ 15 N) of the halophyte plant Salicornia brachiata and physico-chemical characteristics of soils were analysed in order to investigate the relationship of stable isotope distribution in different populations in a growing period in the coastal area of Gujarat, India. Aboveground and belowground biomass of S. brachiata was collected from six different populations at five times (September 2014, November 2014, January 2015, March 2015 and May 2015). The δ 13 C values in aboveground (-30.8 to -23.6 ‰, average: -26.6 ± 0.4 ‰) and belowground biomass (-30.0 to -23.1 ‰, average: -26.3 ± 0.4 ‰) were similar. The δ 13 C values were positively correlated with soil salinity and Na concentration, and negatively correlated with soil mineral nitrogen. The δ 15 N values of aboveground (6.7-16.1 ‰, average: 9.6 ± 0.4 ‰) were comparatively higher than belowground biomass (5.4-13.2 ‰, average: 7.8 ± 0.3 ‰). The δ 15 N values were negatively correlated with soil available P. We conclude that the variation in δ 13 C values of S. brachiata was possibly caused by soil salinity (associated Na content) and N limitation which demonstrates the potential of δ 13 C as an indicator of stress in plants.

Carbon and nitrogen isotopic compositions of particulate organic matter and biogeochemical processes in the eutrophic Danshuei Estuary in northern Taiwan.

PubMed

Liu, Kon-Kee; Kao, Shuh-Ji; Wen, Liang-Saw; Chen, Kuan-Lun

2007-08-15

The Danshuei Estuary is distinctive for the relatively short residence time (1-2 d) of its estuarine water and the very high concentration of ammonia, which is the dominant species of dissolved inorganic nitrogen in the estuary, except near the river mouth. These characteristics make the dynamics of nitrogen cycling distinctively different from previously studied estuaries and result in unusual isotopic compositions of particulate nitrogen (PN). The delta(15)N(PN) values ranging from -16.4 per thousand to 3.8 per thousand lie in the lower end of nitrogen isotopic compositions (-16.4 to +18.7 per thousand) of suspended particulate matter observed in estuaries, while the delta(13)C values of particulate organic carbon (POC) and the C/N (organic carbon to nitrogen) ratios showed rather normal ranges from -25.5 per thousand to -19.0 per thousand and from 6.0 to 11.3, respectively. There were three major types of particulate organic matter (POM) in the estuary: natural terrigenous materials consisting mainly of soils and bedrock-derived sediments, anthropogenic wastes and autochthonous materials from the aquatic system. During the typhoon induced flood period in August 2000, the flux-weighted mean of delta(13)C(POC) values was -24.4 per thousand, that of delta(15)N(PN) values was +2.3 per thousand and that of C/N ratio was 9.3. During non-typhoon periods, the concentration-weighted mean was -23.6 per thousand for delta(13)C(POC), -2.6 per thousand for delta(15)N(PN) and 8.0 for C/N ratio. From the distribution of delta(15)N(PN) values of highly polluted estuarine waters, we identified the waste-dominated samples and calculated their mean properties: delta(13)C(POC) value of -23.6+/-0.7 per thousand, delta(15)N(PN) value of -3.0+/-0.1 per thousand and C/N ratio of 8.0+/-1.4. Using a three end-member mixing model based on delta(15)N(PN) values and C/N ratios, we calculated contributions of the three major allochthonous sources of POC, namely, wastes, soils and bedrock-derived sediments, to the estuary. Their contributions were, respectively, 83%, 12% and 5% under non-typhoon conditions, and 9%, 63% and 28% under typhoon conditions. The autochthonous POM had the most varied isotopic compositions, encompassing the full ranges of delta(13)C(POC) (-25.5 to -19.1 per thousand), delta(15)N(PN) (-16.4-3.8 per thousand) and C/N ratio (6.0-11.3). The heavy end of the carbon isotopic composition reflected the typical marine condition and the lower end the estuarine condition, which probably had elevated concentrations of dissolved inorganic carbon with low delta(13)C values due to input from decomposition of organic matter. The lack of isotopically heavy PN, as found in larger estuaries, was attributed to isotopically light starting materials, namely, anthropogenic wastes, the slow phytoplankton growth within the estuary and the rather short residence time; the latter two factors made (15)N enrichment during ammonia consumption very limited. The most isotopically light PN likely originated from phytoplankton incorporating (15)N-depleted nitrate near the river mouth, where ammonia inhibition of nitrate uptake probably stopped.

Elucidating the nutritional dynamics of fungi using stable isotopes.

PubMed

Mayor, Jordan R; Schuur, Edward A G; Henkel, Terry W

2009-02-01

Mycorrhizal and saprotrophic (SAP) fungi are essential to terrestrial element cycling due to their uptake of mineral nutrients and decomposition of detritus. Linking these ecological roles to specific fungi is necessary to improve our understanding of global nutrient cycling, fungal ecophysiology, and forest ecology. Using discriminant analyses of nitrogen (delta(15)N) and carbon (delta(13)C) isotope values from 813 fungi across 23 sites, we verified collector-based categorizations as either ectomycorrhizal (ECM) or SAP in > 91% of the fungi, and provided probabilistic assignments for an additional 27 fungi of unknown ecological role. As sites ranged from boreal tundra to tropical rainforest, we were able to show that fungal delta(13)C (26 sites) and delta(15)N (32 sites) values could be predicted by climate or latitude as previously shown in plant and soil analyses. Fungal delta(13)C values are likely reflecting differences in C-source between ECM and SAP fungi, whereas (15)N enrichment of ECM fungi relative to SAP fungi suggests that ECM fungi are consistently delivering (15)N depleted N to host trees across a range of ecosystem types.

Stable isotope ratio analysis: A potential analytical tool for the authentication of South African lamb meat.

PubMed

Erasmus, Sara Wilhelmina; Muller, Magdalena; van der Rijst, Marieta; Hoffman, Louwrens Christiaan

2016-02-01

Stable isotope ratios ((13)C/(12)C and (15)N/(14)N) of South African Dorper lambs from farms with different vegetation types were measured by isotope ratio mass spectrometry (IRMS), to evaluate it as a tool for the authentication of origin and feeding regime. Homogenised and defatted meat of the Longissimus lumborum (LL) muscle of lambs from seven different farms was assessed. The δ(13)C values were affected by the origin of the meat, mainly reflecting the diet. The Rûens and Free State farms had the lowest (p ⩽ 0.05) δ(15)N values, followed by the Northern Cape farms, with Hantam Karoo/Calvinia having the highest δ(15)N values. Discriminant analysis showed δ(13)C and δ(15)N differences as promising results for the use of IRMS as a reliable analytical tool for lamb meat authentication. The results suggest that diet, linked to origin, is an important factor to consider regarding region of origin classification for South African lamb. Copyright © 2015 Elsevier Ltd. All rights reserved.

A mass spectrometric method to determine activities of enzymes involved in polyamine catabolism.

PubMed

Moriya, Shunsuke; Iwasaki, Kaori; Samejima, Keijiro; Takao, Koichi; Kohda, Kohfuku; Hiramatsu, Kyoko; Kawakita, Masao

2012-10-20

An analytical method for the determination of three polyamines (putrescine, spermidine, and spermine) and five acetylpolyamines [N(1)-acetylspermidine (N(1)AcSpd), N(8)-acetylspermidine (N(8)AcSpd), N(1)-acetylspermine, N(1),N(8)-diacetylspermidine, and N(1),N(12)-diacetylspermine] involved in the polyamine catabolic pathway has been developed using a hybrid tandem mass spectrometer. Heptafluorobutyryl (HFB) derivatives of these compounds and respective internal standards labeled with stable isotopes were analyzed simultaneously by TOF MS, based on peak areas appearing at appropriate m/z values. The isomers, N(1)AcSpd and N(8)AcSpd were determined from their fragment ions, the acetylamidopropyl and acetylamidobutyl groups, respectively, using MS/MS with (13)C(2)-N(1)AcSpd and (13)C(2)-N(8)AcSpd which have the (13)C(2)-acetyl group as an internal standard. The TOF MS method was successfully applied to measure the activity of enzymes involved in polyamine catabolic pathways, namely N(1)-acetylpolyamine oxidase (APAO), spermine oxidase (SMO), and spermidine/spermine N(1)-acetyltransferase (SSAT). The following natural substrates and products labeled with stable isotopes considering the application to biological samples were identified; for APAO, [4,9,12-(15)N(3)]-N(1)-acetylspermine and [1,4,8-(15)N(3)]spermidine ((15)N(3)-Spd), respectively; for SMO, [1,4,8,12-(15)N(4)]spermine and (15)N(3)-Spd, respectively; and for SSAT, (15)N(3)-Spd and [1,4,8-(15)N(3)]-N(1)-acetylspermidine, respectively. Copyright © 2012 Elsevier B.V. All rights reserved.

Structural investigation of Titan tholins by solution-state 1H, 13C, and 15N NMR: one-dimensional and decoupling experiments.

PubMed

He, Chao; Lin, Guangxin; Upton, Kathleen T; Imanaka, Hiroshi; Smith, Mark A

2012-05-17

Titan, the largest moon of Saturn, is enveloped in a reddish brown organic haze. Titan haze is presumed to be formed from methane and nitrogen (CH(4) and N(2)) in Titan's upper atmosphere through energetic photochemistry and particle bombardment. Though Titan haze has been directly investigated using methods including the Cassini mission, its formation mechanism and the contributing chemical structures and prebiotic potential are still not well developed. We report here the structural investigation of the (13)C and (15)N labeled, simulated Titan haze aerosol (tholin) by solution-state NMR. The one-dimensional (1)H, (13)C, and (15)N NMR spectra and decoupling experiments indicate that the tholin sample contains amine, nitrile, imine, and N-heteroaromatic compounds of tremendous import in understanding complex organic chemistry in anaerobic, extraterrestrial environments.

Stable isotope data from deep-water antipatharians: 400-Year records from the southeastern coast of the United States of America

USGS Publications Warehouse

Williams, B.; Risk, Michael J.; Ross, Steve W.; Sulak, K.J.

2007-01-01

In this study, time-series stable isotope results (δ13C and δ15N) from three deep-water Leiopathes glaberrima(Esper, 1788) specimens Collected off the southeastern Coast of the United States of America and one specimen from the Gulf of Mexico are presented. The specimens were Collected live in 2004 and are estimated to be 200–500 yrs old based on 210Pb measurements and band Counts. The δ13C and δ15N long-term trends are reproducible within and among specimens from a similar location, suggesting a common environmental influence. Three western Atlantic specimens have average δ13C values of −15.7‰, −16.3‰, and −16.1‰, with the most depleted values from the oldest specimen. The oldest specimen records an enrichment in 13C of 0.5‰ corresponding to the Little Ice Age. All three specimens show a depletion of 13C over the past 150 yrs Corresponding to the δ13C Suess Effect. The fourth specimen from the Gulf of Mexico has an average δ13C value of −16.4‰ and shows no trend in13C value with time. All four specimens Contain an enrichment in 15N over the most recent 75 yrs, with the largest enrichment (3‰) in the Gulf of Mexico specimen. This enrichment is likely a result of increased terrestrial effluent (sewage and manure) reaching the offshore specimens.

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

PubMed

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

2013-06-01

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

Stable isotope ratios of marijuana. I. Carbon and nitrogen stable isotopes describe growth conditions.

PubMed

West, Jason B; Hurley, Janet M; Ehleringer, James R

2009-01-01

There remains significant uncertainty in illicit marijuana cultivation. We analyzed the delta(13)C and delta(15)N of 508 domestic samples from known U.S.A. counties, 31 seized from a single location, 5 samples grown in Mexico and Colombia, and 10 northwest border seizures. For a subset, inflorescences and leaves were analyzed separately. These data revealed a strong correspondence, with inflorescences having slightly higher delta(13)C and delta(15)N values than leaves. A framework for interpreting these results is introduced and evaluated. Samples identified as outdoor-grown by delta(13)C were generally recorded as such by the Drug Enforcement Administration (DEA). DEA-classified indoor-grown samples had the most negative delta(13)C values, consistent with indoor cultivation, although many were also in the outdoor-grown domain. Delta(15)N indicated a wide range of fertilizers across the dataset. Samples seized at the single location suggested multiple sources. Northwest border delta(13)C values suggested indoor growth, whereas for the Mexican and Colombian samples they indicated outdoor growth.

Microbes mediate carbon and nitrogen retention in shallow photic sediments

NASA Astrophysics Data System (ADS)

Hardison, A.; Anderson, I.; Canuel, E. A.; Tobias, C.; Veuger, B.

2009-12-01

Sediments in shallow coastal bays are sites of intense biogeochemical cycling facilitated by a complex microbial consortium. Unlike deeper coastal environments, much of the benthos is illuminated by sunlight in these bays. As a result, benthic autotrophs such as benthic microalgae (BMA) and macroalgae play an integral role in nutrient cycling. Investigating pathways of carbon (C) and nitrogen (N) flow through individual compartments within the sediment microbial community has previously proved challenging due to methodological difficulties. However, it is now possible using stable isotopes and microbial biomarkers such as fatty acids and amino acids to track C and N flow through individual microbial pools. We investigated the uptake and retention of C and N by bacteria and BMA in a shallow subtidal system. Using bulk and compound specific isotopic analysis, we traced the pathways of dissolved inorganic 13C and 15N under various treatments: 1) in ambient light or dark, 2) from porewater or water column sources, and 3) in the presence or absence of bloom forming nuisance macroalgae. Excess 13C and 15N in THAAs and excess 13C in total PLFAs showed a strong dependence on light. Enrichment of these pools represents uptake by the microbial community, which can include both autotrophic and heterotrophic components. Higher excess 13C in benthic microalgal fatty acids (C20, C22 PUFAs) provides evidence that benthic microalgae were fixing 13C. Aditionally, the ratio of excess 13C in branched fatty acids to microbial fatty acids (BAR) and excess 13C and 15N in D-Ala to L-Ala (D/L-Ala) were low, suggesting dominance by benthic microalgae over bacteria to total label incorporation. Our results support uptake and retention of C and N by the sediment microbial community and indicate a tight coupling between BMA and bacteria in shallow illuminated systems. This uptake is diminished in the presence of macroalgae, likely due to shading and/or nutrient competition. Therefore, macroalgae reduce the retention of C and N within surface sediments, diminishing the role of the microbial community in nutrient cycling processes.

Estimating tissue-specific discrimination factors and turnover rates of stable isotopes of nitrogen and carbon in the smallnose fanskate Sympterygia bonapartii (Rajidae).

PubMed

Galván, D E; Jañez, J; Irigoyen, A J

2016-08-01

This study aimed to estimate trophic discrimination factors (TDFs) and metabolic turnover rates of nitrogen and carbon stable isotopes in blood and muscle of the smallnose fanskate Sympterygia bonapartii by feeding six adult individuals, maintained in captivity, with a constant diet for 365 days. TDFs were estimated as the difference between δ(13) C or δ(15) N values of the food and the tissues of S. bonapartii after they had reached equilibrium with their diet. The duration of the experiment was enough to reach the equilibrium condition in blood for both elements (estimated time to reach 95% of turnover: C t95%blood  = 150 days, N t95%blood  = 290 days), whilst turnover rates could not be estimated for muscle because of variation among samples. Estimates of Δ(13) C and Δ(15) N values in blood and muscle using all individuals were Δ(13) Cblood = 1·7‰, Δ(13) Cmuscle = 1·3‰, Δ(15) Nblood = 2·5‰ and Δ(15) Nmuscle = 1·5‰, but there was evidence of differences of c.0·4‰ in the Δ(13) C values between sexes. The present values for TDFs and turnover rates constitute the first evidence for dietary switching in batoids based on long-term controlled feeding experiments. Overall, the results showed that S. bonapartii has relatively low turnover rates and isotopic measurements would not track seasonal movements adequately. The estimated Δ(13) C values in S. bonapartii blood and muscle were similar to previous estimations for elasmobranchs and to generally accepted values in bony fishes (Δ(13) C = 1·5‰). For Δ(15) N, the results were similar to published reports for blood but smaller than reports for muscle and notably smaller than the typical values used to estimate trophic position (Δ(15) N c. 3·4‰). Thus, trophic position estimations for elasmobranchs based on typical Δ(15) N values could lead to underestimates of actual trophic positions. Finally, the evidence of differences in TDFs between sexes reveals a need for more targeted research. © 2016 The Fisheries Society of the British Isles.

Positron emitting nuclides and their synthetic incorporation in radiopharmaceuticals. [Labeled with /sup 11/C, /sup 13/N, and /sup 18/F

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

Fowler, J.S.

/sup 11/C, /sup 13/N, and /sup 15/O has potential applicability to the study of metabolism in humans. Problems in the synthesis of radiopharmaceuticals labeled with /sup 11/C, /sup 13/N, and /sup 18/F are described: quality control, radiation exposure, carboxylic acids, glucose, amines, amino acids, nitrosources, fluoroethanol. 54 references. (DLC)

C and N Isotopes in Ostrich Eggshell as Proxies of Paleovegetation and Paleoprecipitation: Extraction, Preservation, and Application to Pleistocene Archaeological Samples

NASA Astrophysics Data System (ADS)

Niespolo, E. M.; Sharp, W. D.; Tryon, C. A.; Faith, J. T.; Miller, M.; Dawson, T. E.

2015-12-01

Paleoenvironmental change is commonly invoked as a factor in the development of modern human behaviors and the successful expansion of H. sapiens out of Africa, and paleoenvironmental information from archaeological sequences is central to addressing such questions. Ostrich eggshell (OES) are common in many African archaeological sequences and may be dated by 14C and U-series methods. In modern ratite eggshells (large flightless birds including the ostrich and emu), the δ13C in eggshell calcite and the δ13C and δ15N in eggshell organic fractions have been shown to vary systematically across climate gradients in South Africa and Australia with δ15N varying inversely with mean annual precipitation, and δ13C varying with the C isotopes of vegetation (1,2). Thus, if primary C and N isotopic signatures are preserved, assemblages of OES can provide dated records of paleovegetation and paleoprecipitation at archaeological sites. Since the C isotopic fractionation between calcite and eggshell organics is constant in modern OES (Δ13Ccalcite-organic = 14.7 ± 1.3‰) (3), evaluating that offset in ancient OES provides a test for preservation of primary isotopic signatures. Johnson et al. (3) showed that OES from Equus Cave (South Africa) retained the expected fractionation for up to 17 ka. We present a new protocol to extract C and N of OES organics for online analysis that preserves pristine δ13C and δ15N values and C and N contents. We find that using sodium hydroxide (NaOH), common to many bone collagen extraction procedures, destroys and degrades the organic component of OES, resulting in low C and N and altered δ13C and δ15N values. Analysis of a series of OES samples directly dated by 14C and U-series from the GvJm-22 rockshelter (Lukenya Hill, Kenya) (4,5) will demonstrate the first application of this protocol to OES from the last ~50,000 yr. 1. Johnson, B.J. et al. (1998) Geochim. Cosmochim. Acta 62, 2451-2461. 2. Newsome, S.D. et al. (2011) Oecologia 167, 1151-1162. 3. Johnson, B.J. et al. (1997) Palaeogeog. Palaeoclimatol. Palaeoecol. 136, 121-137. 4. Tryon, C.A. et al. (2015) PNAS 112, 2682-2687. 5. Sharp, W.D. et al. (2015) Abstract for AfQUA, Cape Town, South Africa.

Relating carbon and nitrogen isotope effects to reaction mechanisms during aerobic or anaerobic degradation of RDX (Hexahydro-1,3,5-Trinitro-1,3,5-Triazine) by pure bacterial cultures

USGS Publications Warehouse

Fuller, Mark E.; Heraty, Linnea J.; Condee, Charles W.; Vainberg, Simon; Sturchio, Neil C.; Böhlke, John Karl; Hatzinger, Paul B.

2016-01-01

Kinetic isotopic fractionation of carbon and nitrogen during RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) biodegradation was investigated with pure bacterial cultures under aerobic and anaerobic conditions. Relatively large bulk enrichments in 15N were observed during biodegradation of RDX via anaerobic ring cleavage (ε15N = −12.7‰ ± 0.8‰) and anaerobic nitro reduction (ε15N = −9.9‰ ± 0.7‰), in comparison to smaller effects during biodegradation via aerobic denitration (ε15N = −2.4‰ ± 0.2‰). 13C enrichment was negligible during aerobic RDX biodegradation (ε13C = −0.8‰ ± 0.5‰) but larger during anaerobic degradation (ε13C = −4.0‰ ± 0.8‰), with modest variability among genera. Dual-isotope ε13C/ε15N analyses indicated that the three biodegradation pathways could be distinguished isotopically from each other and from abiotic degradation mechanisms. Compared to the initial RDX bulk δ15N value of +9‰, δ15N values of the NO2− released from RDX ranged from −7‰ to +2‰ during aerobic biodegradation and from −42‰ to −24‰ during anaerobic biodegradation. Numerical reaction models indicated that N isotope effects of NO2− production were much larger than, but systematically related to, the bulk RDX N isotope effects with different bacteria. Apparent intrinsic ε15N-NO2− values were consistent with an initial denitration pathway in the aerobic experiments and more complex processes of NO2− formation associated with anaerobic ring cleavage. These results indicate the potential for isotopic analysis of residual RDX for the differentiation of degradation pathways and indicate that further efforts to examine the isotopic composition of potential RDX degradation products (e.g., NOx) in the environment are warranted.

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

USGS Publications Warehouse

Johnson, C.A.

1996-01-01

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

Metabolism of α-linolenic acid during incubations with strained bovine rumen contents: products and mechanisms.

PubMed

Honkanen, Anne M; Leskinen, Heidi; Toivonen, Vesa; McKain, Nest; Wallace, R John; Shingfield, Kevin J

2016-06-01

Description of α-linolenic acid (cis-9,cis-12,cis-15-18 : 3, ALA) metabolism in the rumen is incomplete. Ruminal digesta samples were incubated with ALA and buffer containing water or deuterium oxide to investigate the products and mechanisms of ALA biohydrogenation. Geometric Δ9,11,15-18 : 3 isomers were the main intermediates formed from ALA. An increase in the n+1 isotopomers of Δ9,11,15-18 : 3 was due to 2H labelling at C-13. Isomers of Δ9,11,13-18 : 3, cis-7,cis-12,cis-15-18 : 3 and cis-8,cis-12,cis-15-18 : 3 were also formed. No increase in n+1 isotopomers of Δ7,12,15-18 : 3 or Δ8,12,15-18 : 3 was detected. Enrichment in n+2 isotopomers of 18 : 2 products indicated that ALA metabolism continued via the reduction of 18 : 3 intermediates. Isomers of Δ9,11,15-18 : 3 were reduced to Δ11,15-18 : 2 labelled at C-9 and C-13. ALA resulted in the formation of Δ11,13-18 : 2 and Δ12,14-18 : 2 containing multiple 2H labels. Enrichment of the n+3 isotopomer of Δ12,15-18 : 2 was also detected. Metabolism of ALA during incubations with rumen contents occurs by one of three distinct pathways. Formation of Δ9,11,15-18 : 3 appears to be initiated by H abstraction on C-13. Octadecatrienoic intermediates containing cis-12 and cis-15 double bonds are formed without an apparent H exchange with water. Labelling of Δ9,11,13-18 : 3 was inconclusive, suggesting formation by an alternative mechanism. These findings explain the appearance of several bioactive fatty acids in muscle and milk that influence the nutritional value of ruminant-derived foods.

Isotopic and molecular distributions of biochemicals from fresh and buried Rhizophora mangle leaves†

PubMed Central

Smallwood, Barbara J; Wooller, Matthew J; Jacobson, Myrna E; Fogel, Marilyn L

2003-01-01

Rhizophora mangle L. (red mangrove) is the dominant species of mangrove in the Americas. At Twin Cays, Belize (BZ) red mangroves are present in a variety of stand structures (tall >5 m in height, transition ~2–4 m and dwarf ~1–1.5 m). These height differences are coupled with very different stable carbon and nitrogen isotopic values[1] (mean tall δ13C = -28.3‰, δ15N = 0‰; mean tall δ13C = -25.3‰, δ15N = -10‰). To determine the utility of using these distinct isotopic compositions as 'biomarkers' for paleoenvironmental reconstruction of mangrove ecosystems and nutrient availability, we investigated the distribution and isotopic (δ13C and δ15N) composition of different biochemical fractions (water soluble compounds, free lipids, acid hydrolysable compounds, individual amino acids, and the residual un-extractable compounds) in fresh and preserved red mangrove leaves from dwarf and tall trees. The distribution of biochemicals are similar in dwarf and tall red mangrove leaves, suggesting that, regardless of stand structure, red mangroves use nutrients for biosynthesis and metabolism in a similar manner. However, the δ13C and δ15N of the bulk leaf, the biochemical fractions, and seven amino acids can be used to distinguish dwarf and tall trees at Twin Cays, BZ. The data support the theory that the fractionation of carbon and nitrogen occurs prior to or during uptake in dwarf and tall red mangrove trees. Stable carbon and nitrogen isotopes could, therefore, be powerful tools for predicting levels of nutrient limitation at Twin Cays. The δ13C and δ15N of biochemical fractions within preserved leaves, reflect sedimentary cycling and nitrogen immobilization. The δ15N of the immobilized fraction reveals the overlying stand structure at the time of leaf deposition. The isotopic composition of preserved mangrove leaves could yield significant information about changes in ecosystem dynamics, nutrient limitation and past stand structure in mangrove paleoecosystems.

ASE extraction method for simultaneous carbon and nitrogen stable isotope analysis in soft tissues of aquatic organisms.

PubMed

Bodin, Nathalie; Budzinski, Hélène; Le Ménach, Karyn; Tapie, Nathalie

2009-06-08

Since lipids are depleted in 13C relative to proteins and carbohydrates, variations in lipid composition among species and within individuals significantly influence delta13C and may result in misleading ecological interpretations. Whereas lipid extraction before IRMS analysis constitutes a way of stable isotope result lipid-normalisation, such a procedure was given up because of the un-controlled effects of the methods used (i.e., "Bligh & Dyer", Soxhlet, etc.) on delta15N. The aim of this work was to develop a simple, rapid and efficient lipid extraction method allowing for simultaneous C and N stable isotope analysis in the biological soft tissues of aquatic organisms. The goal was to be free from the lipid influence on delta13C values without interfering with delta15N values. For that purpose, the modern automated pressurized liquid extraction technique ASE (accelerated solvent extraction) was selected. Eel muscles representative of a broad range of fat contents were extracted via ASE by using different semi-polar solvents (100% dichloromethane and 80% n-hexane/20% acetone) and by operating at different temperature (ambient temperature and 100 degrees C) and pressure (750 and 1900 psi) conditions. The results were discussed in terms of lipid extraction efficiency as well as delta13C and delta15N variability.

Feeding ecology of pelagic fish larvae and juveniles in slope waters of the Gulf of Mexico.

PubMed

Wells, R J D; Rooker, J R

2009-11-01

Stable isotope ratios of carbon (delta13C) and nitrogen (delta15N) were used to investigate feeding patterns of larval and early juvenile pelagic fishes in slope waters of the Gulf of Mexico. Contribution of organic matter supplied to fishes and trophic position within this pelagic food web was estimated in 2007 and 2008 by comparing dietary signatures of the two main producers in this ecosystem: phytoplankton [based on particulate organic matter (POM)] and Sargassum spp. Stable isotope ratios of POM and pelagic Sargassum spp. were significantly different from one another with delta13C values of POM depleted by 3-6 per thousand and delta15N values enriched by 2 relative to Sargassum spp. Stable isotope ratios were significantly different among the five pelagic fishes examined: blue marlin Makaira nigricans, dolphinfish Coryphaena hippurus, pompano dolphinfish Coryphaena equiselis, sailfish Istiophorus platypterus and swordfish Xiphias gladius. Mean delta13C values ranged almost 2 among fishes and were most depleted in I. platypterus. In addition, mean delta15N values ranged 4-5 with highest mean values found for both C. hippurus and C. equiselis and the lowest mean value for M. nigricans during both years. Increasing delta13C or delta15N with standard length suggested that shifts in trophic position and diet occurred during early life for several species examined. Results of a two-source mixing model suggest approximately an equal contribution of organic matter by both sources (POM=55%; pelagic Sargassum spp.=45%) to the early life stages of pelagic fishes examined. Contribution of organic matter, however, varied among species, and sensitivity analyses indicated that organic source estimates changed from 2 to 13% for a delta(13)C fractionation change of +/-0.25 per thousand or a delta15N fractionation change of +/-1.0 per thousand relative to original fractionation values.

Automated NMR structure determination of stereo-array isotope labeled ubiquitin from minimal sets of spectra using the SAIL-FLYA system.

PubMed

Ikeya, Teppei; Takeda, Mitsuhiro; Yoshida, Hitoshi; Terauchi, Tsutomu; Jee, Jun-Goo; Kainosho, Masatsune; Güntert, Peter

2009-08-01

Stereo-array isotope labeling (SAIL) has been combined with the fully automated NMR structure determination algorithm FLYA to determine the three-dimensional structure of the protein ubiquitin from different sets of input NMR spectra. SAIL provides a complete stereo- and regio-specific pattern of stable isotopes that results in sharper resonance lines and reduced signal overlap, without information loss. Here we show that as a result of the superior quality of the SAIL NMR spectra, reliable, fully automated analyses of the NMR spectra and structure calculations are possible using fewer input spectra than with conventional uniformly 13C/15N-labeled proteins. FLYA calculations with SAIL ubiquitin, using a single three-dimensional "through-bond" spectrum (and 2D HSQC spectra) in addition to the 13C-edited and 15N-edited NOESY spectra for conformational restraints, yielded structures with an accuracy of 0.83-1.15 A for the backbone RMSD to the conventionally determined solution structure of SAIL ubiquitin. NMR structures can thus be determined almost exclusively from the NOESY spectra that yield the conformational restraints, without the need to record many spectra only for determining intermediate, auxiliary data of the chemical shift assignments. The FLYA calculations for this report resulted in 252 ubiquitin structure bundles, obtained with different input data but identical structure calculation and refinement methods. These structures cover the entire range from highly accurate structures to seriously, but not trivially, wrong structures, and thus constitute a valuable database for the substantiation of structure validation methods.

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.

Staphylococcus aureus Peptidoglycan Stem Packing by Rotational-Echo Double Resonance NMR Spectroscopy

PubMed Central

Kim, Sung Joon; Singh, Manmilan; Preobrazhenskaya, Maria; Schaefer, Jacob

2013-01-01

Staphylococcus aureus grown in the presence of an alanine-racemase inhibitor was labeled with D-[1-13C]alanine and L-[15N]alanine to characterize some details of the peptidoglycan tertiary structure. Rotational-echo double-resonance NMR of intact whole cells was used to measure internuclear distances between 13C and 15N of labeled amino acids incorporated in the peptidoglycan, and from those labels to 19F of a glycopeptide drug specifically bound to the peptidoglycan. The observed 13C-15N average distance of 4.1 to 4.4 Å between D- and L-alanines in nearest-neighbor peptide stems is consistent with a local, tightly packed, parallel-stem architecture for a repeating structural motif within the peptidoglycan of S. aureus. PMID:23617832

Spatio-temporal isotopic signatures (δ13 C and δ15 N) reveal that two sympatric West African mullet species do not feed on the same basal production sources.

PubMed

Le Loc'h, F; Durand, J-D; Diop, K; Panfili, J

2015-04-01

Potential trophic competition between two sympatric mullet species, Mugil cephalus and Mugil curema, was explored in the hypersaline estuary of the Saloum Delta (Senegal) using δ(13) C and δ(15) N composition of muscle tissues. Between species, δ(15) N compositions were similar, suggesting a similar trophic level, while the difference in δ(13) C compositions indicated that these species did not feed from exactly the same basal production sources or at least not in the same proportions. This result provides the first evidence of isotopic niche segregation between two limno-benthophageous species belonging to the geographically widespread, and often locally abundant, Mugilidae family. © 2015 The Fisheries Society of the British Isles.

15N fractionation in infrared-dark cloud cores

NASA Astrophysics Data System (ADS)

Zeng, S.; Jiménez-Serra, I.; Cosentino, G.; Viti, S.; Barnes, A. T.; Henshaw, J. D.; Caselli, P.; Fontani, F.; Hily-Blant, P.

2017-07-01

Context. Nitrogen is one of the most abundant elements in the Universe and its 14N/15N isotopic ratio has the potential to provide information about the initial environment in which our Sun formed. Recent findings suggest that the solar system may have formed in a massive cluster since the presence of short-lived radioisotopes in meteorites can only be explained by the influence of a supernova. Aims: We seek to determine the 14N/15N ratio towards a sample of cold and dense cores at the initial stages in their evolution. Methods: We observed the J = 1 → 0 transitions of HCN, H13CN, HC15N, HN13C, and H15NC towards a sample of 22 cores in four infrared-dark clouds (IRDCs) which are believed to be the precursors of high-mass stars and star clusters. Assuming LTE and a temperature of 15 K, the column densities of HCN, H13CN, HC15N, HN13C, and H15NC are calculated and their 14N/15N ratio is determined for each core. Results: The 14N/15N ratios measured in our sample of IRDC cores range between 70 and ≥763 in HCN and between 161 and 541 in HNC. These ratios are consistent with the terrestrial atmosphere (TA) and protosolar nebula (PSN) values, and with the ratios measured in low-mass prestellar cores. However, the 14N/15N ratios measured in cores C1, C3, F1, F2, and G2 do not agree with the results from similar studies towards the same cores using nitrogen bearing molecules with nitrile functional group (-CN) and nitrogen hydrides (-NH) although the ratio spread covers a similar range. Conclusions: Relatively low 14N/15N ratios amongst the four-IRDCs were measured in IRDC G which are comparable to those measured in small cosmomaterials and protoplanetary disks. The low average gas density of this cloud suggests that the gas density, rather than the gas temperature, may be the dominant parameter influencing the initial nitrogen isotopic composition in young PSN. The reduced spectra (FITS files) are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/603/A22

HNCA-TOCSY-CANH experiments with alternate 13C-12C labeling: a set of 3D experiment with unique supra-sequential information for mainchain resonance assignment

PubMed Central

Takeuchi, Koh; Gal, Maayan; Takahashi, Hideo; Shimada, Ichio

2011-01-01

Described here is a set of three-dimensional (3D) NMR experiments that rely on CACA-TOCSY magnetization transfer via the weak 3JCαCα coupling. These pulse sequences, which resemble recently described 13C detected CACA-TOCSY (Takeuchi et al. 2010) experiments, are recorded in 1H2O, and use 1H excitation and detection. These experiments require alternate 13C-12C labeling together with perdeuteration, which allows utilizing the small 3JCαCα scalar coupling that is otherwise masked by the stronger 1JCC couplings in uniformly 13C labeled samples. These new experiments provide a unique assignment ladder-mark that yields bidirectional supra-sequential information and can readily straddle proline residues. Unlike the conventional HNCA experiment, which contains only sequential information to the 13Cα of the preceding residue, the 3D hnCA-TOCSY-caNH experiment can yield sequential correlations to alpha carbons in positions i−1, i + 1 and i−2. Furthermore, the 3D hNca-TOCSY-caNH and Hnca-TOC-SY-caNH experiments, which share the same magnetization pathway but use a different chemical shift encoding, directly couple the 15N-1H spin pair of residue i to adjacent amide protons and nitrogens at positions i−2, i−1, i + 1 and i + 2, respectively. These new experimental features make protein backbone assignments more robust by reducing the degeneracy problem associated with the conventional 3D NMR experiments. PMID:21110064

Backbone resonance assignments of complexes of human voltage-dependent sodium channel NaV1.2 IQ motif peptide bound to apo calmodulin and to the C-domain fragment of apo calmodulin.

PubMed

Mahling, Ryan; Kilpatrick, Adina M; Shea, Madeline A

2017-10-01

Human voltage-gated sodium channel Na V 1.2 has a single pore-forming α-subunit and two transmembrane β-subunits. Expressed primarily in the brain, Na V 1.2 is critical for initiation and propagation of action potentials. Milliseconds after the pore opens, sodium influx is terminated by inactivation processes mediated by regulatory proteins including calmodulin (CaM). Both calcium-free (apo) CaM and calcium-saturated CaM bind tightly to an IQ motif in the C-terminal tail of the α-subunit. Our thermodynamic studies and solution structure (2KXW) of a C-domain fragment of apo 13 C, 15 N- CaM (CaM C ) bound to an unlabeled peptide with the sequence of rat Na V 1.2 IQ motif showed that apo CaM C (a) was necessary and sufficient for binding, and (b) bound more favorably than calcium-saturated CaM C . However, we could not monitor the Na V 1.2 residues directly, and no structure of full-length CaM (including the N-domain of CaM (CaM N )) was determined. To distinguish contributions of CaM N and CaM C , we used solution NMR spectroscopy to assign the backbone resonances of a complex containing a 13 C, 15 N-labeled peptide with the sequence of human Na V 1.2 IQ motif (Na V 1.2 IQp ) bound to apo 13 C, 15 N-CaM or apo 13 C, 15 N-CaM C . Comparing the assignments of apo CaM in complex with Na V 1.2 IQp to those of free apo CaM showed that residues within CaM C were significantly perturbed, while residues within CaM N were essentially unchanged. The chemical shifts of residues in Na V 1.2 IQp and in the C-domain of CaM were nearly identical regardless of whether CaM N was covalently linked to CaM C . This suggests that CaM N does not influence apo CaM binding to Na V 1.2 IQp .

Trophic shift in young-of-the-year Mugilidae during salt-marsh colonization.

PubMed

Lebreton, B; Richard, P; Guillou, G; Blanchard, G F

2013-04-01

This study investigated the trophic shift of young-of-the-year (YOY) thinlip grey mullet Liza ramada and golden grey mullet Liza aurata during their recruitment in a salt marsh located on the European Atlantic Ocean coast. Stable-isotope signatures (δ(13) C and δ(15) N) of the fishes followed a pattern, having enrichments in (13) C and (15) N with increasing fork length (LF ): δ(13) C in fishes < 30 mm ranged from -19.5 to -15.0‰, whereas in fishes > 30 mm δ(13) C ranged from -15.8 to -12.7‰, closer to the level in salt-marsh food resources. Large differences between the δ(15) N values of mugilids and those of food sources (6·0‰ on average) showed that YOY are secondary consumers, similar to older individuals, when feeding in the salt marsh. YOY mugilids shift from browsing on pelagic prey to grazing on benthic resources from the salt marsh before reaching 30 mm LF. The results highlight the role of European salt marshes as nurseries for juvenile mugilids. © 2013 The Authors. Journal of Fish Biology © 2013 The Fisheries Society of the British Isles.

Kinetic commitment in the catalysis of glutamine synthesis by GS1 from Arabidopsis using 14N/15N and solvent isotope effects.

PubMed

Mauve, Caroline; Giraud, Nicolas; Boex-Fontvieille, Edouard R A; Antheaume, Ingrid; Tea, Illa; Tcherkez, Guillaume

2016-11-01

Glutamine synthetase (GS, EC 6.3.1.2) catalyzes the production of glutamine from glutamate, ammonium and ATP. Although being essential in plants for N assimilation and recycling, kinetic commitments and transition states of the reaction have not been clearly established yet. Here, we examined 12 C/ 13 C, 14 N/ 15 N and H 2 O/D 2 O isotope effects in Arabidopsis GS1 catalysis and compared to the prokaryotic (Escherichia coli) enzyme. A 14 N/ 15 N isotope effect ( 15 V/K ≈ 1.015, with respect to substrate NH 4 + ) was observed in the prokaryotic enzyme, indicating that ammonium utilization (deprotonation and/or amidation) was partially rate-limiting. In the plant enzyme, the isotope effect was inverse ( 15 V/K = 0.965), suggesting that the reaction intermediate is involved in an amidation-deamidation equilibrium favoring 15 N. There was no 12 C/ 13 C kinetic isotope effect ( 13 V/K = 1.000), suggesting that the amidation step of the catalytic cycle involves a transition state with minimal alteration of overall force constants at the C-5 carbon. Surprisingly, the solvent isotope effect was found to be inverse, that is, with a higher turn-over rate in heavy water ( D V ≈ 0.5), showing that restructuration of the active site due to displacement of H 2 O by D 2 O facilitates the processing of intermediates. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

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

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

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 bothmore » 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.« less

THE POLARIZATION OF NEUTRONS FROM THE C$sup 12$(d,n) N$sup 13$ REACTION

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

Budzanowski, A.; Grotowski, K.; Niewodniczanski, H.

1959-01-01

The polarization of neutroni emitted irom the stripping reaction C/sup 12/(d,n)N/sup 13/ was investigated at the reaction angle theta /sub lab/ = 15 deg and deuteron energy E/sub d/ = I2.9 Mev. The polarization of neutrons connected with the 3.56 Mev energy- level in N/sup 13/ nucleus was found to be - (0.39 plus or minus 0.11). (auth)

Gas chromatography and isotope ratio mass spectrometry of Pinot Noir wine volatile compounds (δ13C) and solid residues (δ13C, δ15N) for the reassessment of vineyard water-status.

PubMed

Spangenberg, Jorge E; Vogiatzaki, Maria; Zufferey, Vivian

2017-09-29

This paper describes a novel approach to reassess the water status in vineyards based on compound-specific isotope analysis (CSIA) of wine volatile organic compounds (δ 13 C VOC/VPDB ) and bulk carbon and nitrogen isotopes, and the C/N molar ratios of the wine solid residues (δ 13 C SR/VPDB , δ 15 N SR/Air-N2 ). These analyses link gas chromatography/combustion and elemental analysis to isotope ratio mass spectrometry (GC/C/IRMS, EA/IRMS). Field-grown cultivars of Pinot Noir grapevines were exposed during six growing seasons (2009-2014) to controlled soil water availability, while maintaining identical the other environmental variables and agricultural techniques. Wines were produced from the grapes by the same oenological protocol. This permitted for the assessment of the effects in the biochemistry of wines solely induced by the changes in the plant-soil water status. This mimicked the more recurrent and prolonged periods of soil water deficiency due to climate changes. Water stress in grapevine was assessed by the measurement of the predawn leaf water potential (Ψ pd ) and the stable carbon isotope composition of the berry sugars during harvest (must sugars). For quantitation purposes and the normalization of the measured stable carbon isotope ratios of the VOCs, the wine samples were spiked with three standard compounds with known concentration and δ 13 C VPDB values. VOCs were extracted by liquid-liquid extraction and analyzed by gas chromatography/flame ionization detection (GC/FID), gas chromatography/mass spectrometry (GC/MS), and GC/C/IRMS. δ 13 C values were obtained for eighteen VOCs. The solid residues were obtained by freeze-drying wine aliquots and were analyzed for their C and N content and isotope composition by EA/IRMS. All the isotopic ratios (δ 13 C SR , δ 15 N SR , δ 13 C VOC ) are highly correlated with the Ψ pd values, indicating that the proposed gas chromatography and isotope ratio mass spectrometry approach is a useful tool to assess the changes in the water status of grapevine cultivars in different terroirs. The combined analytical approach was used for the first time to complement the assessment of soil water availability effects on the grapevine. The δ 13 C values of the volatile compounds helped confirm (or establish) their main source(s) and biosynthetic pathway(s). Importantly, we also show for the first time that the combination of C/N and δ 15 N values of freeze-dried wines have an unexplored potential for the study of nitrogen dynamics in soil/grape/wine systems. Copyright © 2017 Elsevier B.V. All rights reserved.

Understanding gas shales using inorganic, ternary geochemical systematics.

NASA Astrophysics Data System (ADS)

Basu, Sudeshna; Jones, Adrian; Verchovsky, Alexander

2016-04-01

We have developed a new approach of simultaneous analyses of carbon, nitrogen and noble gases, for isotopic and elemental compositions in bulk shales from different depths (11785 to 11909 feet) of a core from the Haynesville Bossier formation to decouple the different trapped components. This is preceded by major, minor and trace elemental analyses to understand their paleo productivity, tectonic and redox conditions of deposition as well as constraining their alteration and weathering. 5 to 10 mg of samples have been combusted from 200-1200°C in incremental steps of 100°C. Based on δ13C, we identify both marine+lacustrine (δ13C ~ -25 ‰, C/N ~ 5) and minor continental organic matter (δ13C ~ -27 ‰, C/N ~ 60) in the samples, in agreement with observations from elemental compositions. Extremely depleted δ13C of ≤ -34 ‰ in some temperature steps, can be attributed to methanogenesis. Two carbonate populations, primary (δ13C ~ 0 to 2 ‰) and diagenetic (δ13C ~ -13 to -11 ‰) can also be identified. We have been able to identify the multiple C components present in the samples, including very minor ones, without resorting to acid treatment. The bulk N δ15N values vary from -1.2to +6.4 ‰, but show a wide range from -15 to 15 ‰ within individual steps. By suitable modelling, we constrain the primary δ15N to be 5 to 8 ‰, identifiable in very high temperature steps of heating. This is possible if there is penetration of hot fluids that eliminates organic N along a reaction front leaving it fractionated, but leaves behind an unreacted core of residual nitrogen unaffected by isotopic fractionation (Boudou et al., 2008). Our study indicates that using bulk N values as primary signatures to constrain the redox conditions of deposition or thermal maturity of shales as is the practice, should be done with caution. Simultaneously obtained noble gases were used to constrain gas retention in the samples. Deviations of measured 4He/40Ar* (where 40Ar* represents radiogenic 40Ar after correcting for contribution from atmospheric Ar) from expected values has been used to monitor gas loss by degassing. Boudou, J., Schimmelmann, A., Ader, M., Mastalerz, M., Sebilo, M., Gengembre, L.,2008. Organic nitrogen chemistry during low grade metamorphism. Geochimica Cosmochimica Acta 72, 1199-1221.

Holocene changes in the trophic ecology of an apex marine predator in the South Atlantic Ocean.

PubMed

Vales, Damián G; Cardona, Luis; Zangrando, Atilio F; Borella, Florencia; Saporiti, Fabiana; Goodall, R Natalie P; de Oliveira, Larissa Rosa; Crespo, Enrique A

2017-02-01

Predators may modify their diets as a result of both anthropogenic and natural environmental changes. Stable isotope ratios of nitrogen and carbon in bone collagen have been used to reconstruct the foraging ecology of South American fur seals (Arctocephalus australis) in the southwestern South Atlantic Ocean since the Middle Holocene, a region inhabited by hunter-gatherers by millennia and modified by two centuries of whaling, sealing and fishing. Results suggest that the isotopic niche of fur seals from Patagonia has not changed over the last two millennia (average for the period: δ 13 C 2200-0BP  = -13.4 ± 0.5‰, δ 15 N 2200-0BP  = 20.6 ± 1.1‰). Conversely, Middle Holocene fur seals fed more pelagically than their modern conspecifics in the Río de la Plata region (δ 13 C 7000BP  = -15.9 ± 0.6‰ vs. δ 13 C PRESENT  = -13.5 ± 0.8‰) and Tierra del Fuego (δ 13 C 6400-4300BP  = -15.4 ± 0.5‰ vs. δ 13 C PRESENT  = -13.2 ± 0.7‰). In the latter region, Middle Holocene fur seals also fed at a higher trophic level than their modern counterparts (δ 15 N 6400-4300BP  = 20.5 ± 0.5‰ vs. δ 15 N PRESENT  = 19.0 ± 1.6‰). Nevertheless, a major dietary shift was observed in fur seals from Tierra del Fuego during the nineteenth century (δ 13 C 100BP  = -17.2 ± 0.3‰, δ 15 N 100BP  = 18.6 ± 0.7‰), when marine primary productivity plummeted and the fur seal population was decimated by sealing. Disentangling the relative roles of natural and anthropogenic factors in explaining this dietary shift is difficult, but certainly the trophic position of fur seals has changed through the Holocene in some South Atlantic regions.

Effects of Fire on the Plant-Soil Interactions in Northern Chihuahuan Desert

NASA Astrophysics Data System (ADS)

Wang, G.; Li, J. J.; Ravi, S.; Sankey, J. B.; Theiling, B. P.; Dukes, D.; Gonzales, H. B.; Van Pelt, R. S.

2017-12-01

Desert grasslands in the southwestern US have undergone dramatic land degradation with woody shrub encroachment over the last 150 years. Soil carbon (C), nitrogen (N) and other soil nutrients are redistributed among shrubs, grasses, and bare interspaces during encroachment. Several studies suggest that periodic fire favors the homogenization of soil resources and can provide a certain form of reversibility for the shrub-grass transition. In this study, we used manipulative field experiments to investigate the influence of fire on the isotope composition of C (δ13C) and N (δ15N) in bare interspace, grass and shrub microsites. Replicated burned and control (unburned) experimental plots (5 m × 5 m) were set up in a desert grassland in northern Chihuahuan Desert in March 2016. In each plot, a total of 50 randomly-distributed surface soil samples, with their microsite types accurately recorded, were collected twice per year in March and June (before and after the windy season). δ13C and δ15N in the soil samples were analyzed. Our results show that fire has changed soil δ13C and δ15N after two windy seasons, especially in the shrub microsite. For example, δ13C increased from -18.8‰ to -17.0‰ after a windy season in soils under burned shrub canopies, and increased to -14.3‰ in Mar. 2017, one year after the prescribed fire. In contrast, it changed notably from -14.6‰ to -17.6‰ under shrub canopies in the control plot during the same period of time. For soil δ15N, it decreased slightly from 6.1‰ to 5.6‰ within a year after the prescribed fire in shrub microsite, and a comparable decline was also observed in the same type of microsite of the control plot. Because the average δ13C value of C4 plant tissue (-12‰) is distinct from C3 plants (-26‰), the increase of soil δ13C suggests that the relative contribution of soil organic matter under shrub canopies from shrubs (C3 plants) decreased after a burning event compared to grasses (C4 plants). The insignificant change of soil δ15N in shrub microsite indicates that soil mineralization rates and plant N uptake under shrub canopies may not be substantially altered by the prescribed fire. Our results highlighted that fire can change the resource interactions between soil and plants, which may further affect the shrub encroachment process as well as the dynamics of grassland-shrubland ecosystem.

Food web structure of the epibenthic and infaunal invertebrates on the Catalan slope (NW Mediterranean): Evidence from δ 13C and δ 15N analysis

NASA Astrophysics Data System (ADS)

Fanelli, E.; Papiol, V.; Cartes, J. E.; Rumolo, P.; Brunet, C.; Sprovieri, M.

2011-01-01

The food-web structure of the epibenthic and infaunal invertebrates on the continental slope of the Catalan Sea (Balearic basin, NW Mediterranean) was investigated using carbon and nitrogen stable isotopes on a total of 34 species, and HPLC pigment analyses for three key species. Samples were collected close to Barcelona (NE Iberian Peninsula), between 650 and 800 m depth and between February 2007 and February 2008. Mean δ 13C values ranged from -21.0‰ (small Calocaris macandreae and Amphipholis squamata) to -14.5‰ ( Sipunculus norvegicus). Values of δ 15N ranged from 4.0‰ ( A. squamata) to 12.1‰ ( Molpadia musculus). The stable isotope ratios of benthic fauna displayed a continuum of values (e.g. δ 15N range of 8‰), confirming a wide spectrum of feeding strategies (from active suspension feeders to predators) and complex food webs. According to the available information on diets of benthic fauna, the lowest values were found for surface deposit feeders (small C. macandrae and the two ophiuroids A. squamata and Amphiura chiajei) and active suspension feeders ( Abra longicallus and Scalpellum scalpellum) feeding on different sizes of particulate organic matter (POM), among which small particles may exhibit lower δ 15N. High annual mean δ 15N values were found among sub-surface deposit feeders, exploiting refractory or frequently recycled organic matter that is enriched in δ 15N. Carnivorous polychaetes ( Nephtys spp., Oenonidae and Polynoidae) and large decapods ( Geryon longipes and Paromola cuvieri) also displayed high δ 15N values. δ 13C ranges were particularly wide among surface deposit feeders (ranging from -21.0‰ to -16.4‰), suggesting exploitation of POM of both terrigenous and oceanic origins. Correlation between δ 13C and δ 15N was generally weak, indicating multiple carbon sources, likely due to the consumption of different kinds of sinking particles (e.g. marine snow, phytodetritus, etc.), sedimented and frequently recycled POM, together with macrophyte remains. The stronger δ 13C-δ 15N correlations found in February and April suggest that during the period of water column homogeneization (winter-spring), the benthic community was sustained by phytodetritus inputs originating from the peak of surface primary production in February. Conversely, weaker δ 13C-δ 15N correlations were observed during the period of water column stratification (beginning in June-July), suggesting that the benthic community in this period was sustained, with a delay of ca. 2/3 months, by multiple carbon sources including continental inputs from river discharge (with the maxima in April-May). Thus both advective and vertical fluxes seem to be food sources for benthos on the Catalonian slope. Pigments in the guts of key species were generally degraded, and only the active suspension feeder A. longicallus ingested fresh chlorophyll during periods of high primary production at the surface (February and April 2007).

Carbon and nitrogen stable isotope analysis of three types of oyster tissue in an impacted estuary

NASA Astrophysics Data System (ADS)

Piola, Richard F.; Moore, Stephanie K.; Suthers, Iain M.

2006-01-01

The stable isotope ratios of carbon ( δ13C) and nitrogen ( δ15N) of the muscle, ctenidia and viscera of the Sydney rock oyster, Saccostrea glomerata, showed the dilution and assimilation of tertiary treated sewage along an estuarine gradient. The enriched 15N values of oyster ctenidia and viscera from within 50 m of the sewage outfall indicated the use of 15N-enriched tertiary treated sewage effluent (16 ± 2.3‰) as a nutrient source. The effect of sewage nitrogen on oyster δ15N was localised, with oysters 5 km upstream and downstream of the outfall not significantly enriched. Viscera δ15N was most sensitive to sewage nutrients and δ13C significantly defined an ocean-to-estuarine gradient. High variance in isotope ratios of viscera compromised its use as an indicator of anthropogenic nutrients, and this also reduced the utility of whole-body stable isotope ratios. Ctenidia was the most useful indicator tissue of sewage discharge at the scale of this study, being consistently and significantly enriched in δ15N close to the sewage outfall and δ13C clearly defined an estuarine gradient with less internal variability than viscera. Muscle δ15N was least sensitive to sewage effluent and showed the least variability, making it more suited to investigations of anthropogenic nutrient enrichment over larger spatio-temporal scales.

Tracking the flow of bacterially derived 13C and 15N through soil faunal feeding channels.

PubMed

Crotty, F V; Blackshaw, R P; Murray, P J

2011-06-15

The soil food web has been referred to as a 'black box', a 'poor man's tropical rainforest' and an 'enigma', due to its opacity, diversity and the limited insight into feeding specificity. Here we investigate the flow of C and N through the soil food web as a way to gain understanding of the feeding interactions occurring. A bacterium, Pseudomonas lurida, was introduced to soil cores from two different habitats, a grassland and a woodland with the same soil type, enriched to 99 atom% in (13)C and (15)N, to trace the flow of bacterial C and N through the soil food web. Throughout the experiment the soil remained enriched in (13)C and (15)N. Almost all the invertebrates tested gained C and N enrichment indicative of the labelled bacteria, implying that bacterial feeding is a common mechanism within the soil. Only three groups were significantly enriched in both (13)C and (15)N in both habitats. These were Collembola (Entomobryomorpha), Acari (Oribatida), and Nematoda, indicating that these organisms are consuming the most bacteria within both systems. When the invertebrates were grouped into hypothesised trophic levels, those considered secondary decomposers were gaining the most enrichment across all invertebrates tested. This enrichment was also high in the micro-predators within the soil, implying that their main food source was the secondary decomposers, particularly the Collembola. Using an enriched bacterium to track the trophic transfer between organisms within the soil food web is a novel way of empirically showing that interactions are occurring, which normally cannot be seen. Copyright © 2011 John Wiley & Sons, Ltd.

Seasonal variations and sources of sedimentary organic carbon in Tokyo Bay.

PubMed

Kubo, Atsushi; Kanda, Jota

2017-01-30

Total organic carbon (TOC), total nitrogen (TN) contents, their stable C and N isotope ratio (δ 13 C and δ 15 N), and chlorophyll a ([Chl a] sed ) of surface sediments were investigated monthly to identify the seasonal variations and sources of organic matter in Tokyo Bay. The sedimentary TOC (TOC sed ) and TN (TN sed ) contents, and the sedimentary δ 13 C and δ 15 N (δ 13 C sed and δ 15 N sed ) values were higher in summer than other seasons. The seasonal variations were controlled by high primary production in the water column and hypoxic water in the bottom water during summer. The fraction of terrestrial and marine derived organic matter was estimated by Bayesian mixing model using stable isotope data and TOC/TN ratio. Surface sediments in Tokyo Bay are dominated by marine derived organic matter, which accounts for about 69±5% of TOC sed . Copyright © 2016 Elsevier Ltd. All rights reserved.

Sewage derive [sup 15]N in the Baltic traced in fucus

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

Hobbie, J.E.; Fry, B.; Larsson, U.

Himmerfjarden, a fjord-like bay on the eastern shore of the Baltic, receives treated sewage from 250,000 inhabitants. Because the inorganic N in the effluent is enriched in [sup 15]N through denitrification, nitrification, and ammonia volatilization, an analysis of the distribution of [sup 15]N in the Bay tells how far from the source the sewage nitrogen moves. The attached macroalga Fucus vesiculosus was collected in early May from rocky shore at 0-0.5 m depth and the [sup 15]N content of the tips of the fronds analyzed. This N represents uptake and storage during the previous six months and growth during Marchmore » and April. The [delta][sup 15]N was uniformly high (11-13[per thousand]) in the main body of the Bay within 15 km from the sewage source. Beyond 15 km values decreased with distance to a low of 4.6[per thousand] at 35 km, where the Bay ends and the coastal waters begin. Using the 11-13 and 4.6[per thousand] as endmembers, the percentage of sewage N making up the Fucus at any point may be calculated. The [delta][sub 15]N of particulate organic matter in the offshore Baltic waters was around 0[per thousand] and Fucus had an [delta][sup 15]N about 1.5[per thousand] higher than the POM. From this and other evidence we conclude that there is a belt of coastal water with an elevated [delta][sup 15]N lying along the east coast of the Baltic. This presumably derives from sewage and perhaps from agriculture and is potentially of use as a tracer of coastal zone/pelagic zone interactions.« less

Application of Nitrogen and Carbon Stable Isotopes (δ15N and δ13C) to Quantify Food Chain Length and Trophic Structure

PubMed Central

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 (δ15N) and carbon (δ13C) 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 δ15N, and carbon range (CR) using δ13C, 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 δ15N or δ13C from source to consumer) between trophic levels and among food chains. δ15N 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. δ13C 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 δ13C 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 ecological systems. PMID:24676331

Blood-specific isotopic discrimination factors in the Magellanic penguin (Spheniscus magellanicus).

PubMed

Ciancio, Javier E; Righi, Carina; Faiella, Adrián; Frere, Esteban

2016-08-30

The use of stable isotopes for ecological studies has increased exponentially in recent years. Isotopic trophic studies are based on the assumption that animals are what they eat plus a discrimination factor. The discrimination factor is affected by many variables and can be determined empirically. The Magellanic penguin is a highly abundant marine bird that plays a key role in the southern oceans. This study provides the first estimation of the Magellanic penguin blood discrimination factor for (13) C and (15) N. A two and a half month feeding experiment was performed, in which ten captive penguins were fed their main natural prey (anchovy Engraulis anchoita). The discrimination factors were estimated by comparing anchovy δ(13) C and δ(15) N values (obtained with isotope ratio mass spectrometry using lipid-extracted and bulk anchovy muscle) with penguin blood δ(13) C and δ(15) N values. Penguin blood was shown to be enriched, compared with anchovies, for (13) C and (15) N. No changes were observed in the stable isotope ratios of anchovies and discrimination factors during the experiment. The overall discrimination factors were 0.93 ± 0.12 (bulk) and 0.41 ± 0.12 (lipid-free) for (13) C; and 2.81 ± 0.17 (bulk) and 2.31 ± 0.17 (lipid-free) for (15) N. Having an accurate discrimination factor for the studied species is key in any trophic or food web isotopic study. Comparisons of estimated diet-to-blood discrimination factors with published values of aquatic piscivore birds showed that the (13) C discrimination factor is particularly variable, and therefore ecologists should be cautious when using a surrogate value from other species. In this study, the Magellanic penguin discrimination factor of a tissue that does not require euthanasia was obtained, a fundamental input for trophic isotopic modeling of the species. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Isotopic niches of fishes in coastal, neritic and oceanic waters off Adélie land, Antarctica

NASA Astrophysics Data System (ADS)

Cherel, Yves; Koubbi, Philippe; Giraldo, Carolina; Penot, Florian; Tavernier, Eric; Moteki, Masato; Ozouf-Costaz, Catherine; Causse, Romain; Chartier, Amélie; Hosie, Graham

2011-08-01

We used the stable isotope method to investigate the ecological niches of Antarctic fishes, with δ 13C and δ 15N as proxies of fish habitats and dietary habits, respectively. Muscle isotopic signature was measured for each of 237 delipidated tissue samples from 27 fish species collected offshore Adélie Land, East Antarctica. Overall, δ 13C values ranged from -25.3‰ to -18.2‰, thus allowing characterizing of the fish habitats, with inshore/benthic species having more positive δ 13C signatures than offshore/pelagic ones. No clear difference in the δ 13C values of pelagic fishes was found between species living in neritic and oceanic waters. Overall, the δ 15N signatures of neritic pelagic and epibenthic fishes encompassed ˜1.0 trophic level (3.1‰), a higher difference than that (1.4‰) found within the oceanic assemblage. Fishes with the lowest and highest δ 15N values are primarily invertebrate- and fish-eaters, respectively. The isotopic niches of fishes illustrate the different mechanisms allowing coexistence, with most fishes segregating at least by one of the two niche axes (δ 13C and δ 15N). Muscle isotopic values also document interindividual foraging specialization over the long-term in coastal benthic fishes, but not in more offshore pelagic species. Finally, the δ 15N signatures of fishes overlap with those of penguins and seals, indicating that seabirds and marine mammals share the upper levels of the Antarctic pelagic ecosystem with some large fish species. In conclusion, the concept of isotopic niche is a powerful tool to investigate various aspects of the ecological niche of Antarctic fishes, thus complementing the use of other conventional and non-conventional approaches.

Development of Simultaneous in situ Analysis of Carbon and Nitrogen Isotope Ratios in the Organic Matter by Secondary Ion Mass Spectrometry

NASA Astrophysics Data System (ADS)

Ishida, A.; Kitajima, K.; Williford, K. H.; Kakegawa, T.; Valley, J. W.

2017-12-01

An in-situ analytical method for simultaneous analysis of carbon and nitrogen isotope ratios in organic matter was developed for 12 μm spots by secondary ion mass spectrometry (IMS 1280 at WiscSIMS). Secondary ions of 12C12C-, 12C13C-, 12C14N-, and 12C15N- are simultaneously measured by three Faraday cups and one electron multiplier. Ions of 12C12CH- are measured to monitor hydride interferences. The spot-by-spot reproducibility of δ13C and δ15N values of UWLA-1 anthracite standard (95.7 wt%C and 1.2 wt%N), which was selected as a running reference material, are 0.16‰ and 0.56‰ (2SD), respectively. A negative correlation is observed between the instrumental mass fractionation (mass bias) of carbon and 12C12CH-/12C12C- ratios of examined reference materials. In contrast, there is no correlation of mass bias and hydride cps for nitrogen isotope measurements, suggesting the mass bias of nitrogen can be determined independently of the hydrogen. Values of 22 individual globules of organic matter in a carbonate rock from the 1.9 Ga Gunflint Formation, determined by the new procedure, average δ13C = -33.5 ± 0.25‰ (VPDB) and δ15N = +5.2 ± 0.81‰ (Air). Values of δ13C of both SIMS and bulk kerogen analyses are consistent within analytical error. In contrast, a difference of 1.7‰, which is larger than the 2SD error of each analysis, is observed in δ15N values for in situ vs. bulk kerogen analyses (δ15Nbulk = +6.9 ± 0.6‰). This difference in δ15N might be caused by the preferential removal of low-δ15N components in the organic matter by HCl/HF acid treatment during the bulk kerogen isolation. Simultaneous analyses of carbon and nitrogen in the same micro-volume of organic matter in Precambrian sedimentary rocks will allow correlations with textures and mineralogical occurrences, which will provide more detailed constraints on environments and life of the early Earth. Furthermore, this method is applicable to a wide variety of other research fields, including nutrient distributions in the microstructure of plants and animals, heterogeneous isotope distributions of organic matter in meteorites, maturity of coal, and genesis of diamonds, leading us to understand the evolution of the Earth system.

Stellar Origin of {sup 15}N-rich Presolar SiC Grains of Type AB: Supernovae with Explosive Hydrogen Burning

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

Liu, Nan; Nittler, Larry R.; Alexander, Conel M. O’D.

We report C, N, and Si isotopic data for 59 highly {sup 13}C-enriched presolar submicron- to micron-sized SiC grains from the Murchison meteorite, including eight putative nova grains (PNGs) and 29 {sup 15}N-rich ({sup 14}N/{sup 15}N ≤ solar) AB grains, and their Mg–Al, S, and Ca–Ti isotope data when available. These 37 grains are enriched in {sup 13}C, {sup 15}N, and {sup 26}Al with the PNGs showing more extreme enhancements. The {sup 15}N-rich AB grains show systematically higher {sup 26}Al and {sup 30}Si excesses than the {sup 14}N-rich AB grains. Thus, we propose to divide the AB grains into groupsmore » 1 ({sup 14}N/{sup 15}N < solar) and 2 ({sup 14}N/{sup 15}N ≥ solar). For the first time, we have obtained both S and Ti isotopic data for five AB1 grains and one PNG and found {sup 32}S and/or {sup 50}Ti enhancements. Interestingly, one AB1 grain had the largest {sup 32}S and {sup 50}Ti excesses, strongly suggesting a neutron-capture nucleosynthetic origin of the {sup 32}S excess and thus the initial presence of radiogenic {sup 32}Si ( t {sub 1/2} = 153 years). More importantly, we found that the {sup 15}N and {sup 26}Al excesses of AB1 grains form a trend that extends to the region in the N–Al isotope plot occupied by C2 grains, strongly indicating a common stellar origin for both AB1 and C2 grains. Comparison of supernova models with the AB1 and C2 grain data indicates that these grains came from supernovae that experienced H ingestion into the He/C zones of their progenitors.« less

Sediment geochemistry as potential sea-level indicators to assess coseismic vertical displacements above the Alaska-Aleutian megathrust

NASA Astrophysics Data System (ADS)

Bender, A. M.; Witter, R. C.; Munk, L. A.

2012-12-01

Nearly the entire 4000-km-long Alaska-Aleutian megathrust has ruptured in large or great (Mw ≥8) earthquakes in the past 100 years, yet paleoseismic records of earlier events are only documented east of Kodiak Is. in the region of the 1964 Alaska earthquake. The Mw 9.2 1964 earthquake dropped the coast along Cook Inlet and Turnagain Arm by ≤1.8 m and raised shore platforms around Prince William Sound by ≤3 m. Evidence of sudden (coseismic) vertical displacements during megathrust earthquakes are archived in coastal sediments as sharp stratigraphic contacts that record rapid relative sea-level (RSL) changes. We use geochemical analyses of coastal sediments to detect sudden RSL changes at 2 sites above the Alaska-Aleutian megathrust. One site on Knik Arm near Anchorage subsided ~0.6 m during the 1964 earthquake. The other site overlies the Shumagin Islands segment of the megathrust, without rupture since before 1903. Relative to terrestrial sources of sediment, marine sources should be enriched in δ13C, δ15N, and have higher C:N, and Cl- concentrations. Our analyses will test whether these geochemical proxies can provide evidence for sudden RSL change across stratigraphic contacts that record coseismic uplift or subsidence. Coseismic subsidence should be represented by contacts that place sediment with enriched δ13C, δ15N signatures, elevated C:N and Cl- concentrations over sediment with lower values of these geochemical proxies and the reverse for coseismic uplift. A 1-2 m tall, ~0.5-km-long bluff along Knik Arm exposes three buried wetland soils overlain by gray mud. The soils become faint and pinch out to the northeast near a large tidal channel. Other studies of similar buried soils at adjacent sites suggest the youngest soil at Knik Arm subsided in 1964. 14C analyses of plant fossils in two older soils will provide age estimates for earlier events. We will apply the proposed geochemical methods to 20 samples collected along a forested upland to tidal mud flat transect to distinguish terrestrial from marine sediment. On Simeonof Is., stratigraphy beneath a peat bog adjacent to a tidal lagoon consists of basal marine sand overlain by ~0.6-1.5 m of peat. The presence of Arachnoidiscus japonicas, benthic marine diatom, implies a marine sand source. Sphagnum spp. and absence of marine foraminifera indicate freshwater peat. We analyzed δ13C, δ15N, and C:N from bulk sediment, and Cl- from water soluble fraction of sediment in a 1.3-m bog core. Freshwater peat at depths of 0.0-26.0, and 33.0-78.5 cm have δ13C ranging from -25.02 to -27.35 ‰, δ15N from 3.30-9.93‰, C:N of 10.16-17.89, and Cl- concentrations of 0.9-25.9 mg/L. Sand dominated intervals at 26.0-33.0, and 78.5-130 cm have δ13C ranging from -17.24 to -26.50‰, δ15N from 8.30-11.11‰ , C:N of 0.30-29.6 and Cl- concentrations of 0.7-19.3 mg/L. The data also indicate that average δ13C and δ15N values are enriched in marine sand relative to freshwater peat, respectively by 3.27‰ and 3.10‰. Also C:N ratios and Cl- concentrations are lower in marine sand, respectively by 23.1 and 0.1 mg/L. Hence, δ13C and δ15N show promise as geochemical proxies to distinguish terrestrial from marine sediment for future Alaska-Aleutian paleoseismic studies west of Kodiak Is.

From the epipelagic zone to the abyss: Trophic structure at two seamounts in the subtropical and tropical Eastern Atlantic - Part I zooplankton and micronekton

NASA Astrophysics Data System (ADS)

Denda, Anneke; Stefanowitsch, Benjamin; Christiansen, Bernd

2017-12-01

Specific mechanisms, driving trophic interactions within the pelagic community may be highly variable in different seamount systems. This study investigated the trophic structure of zooplankton and micronekton above and around Ampère and Senghor, two shallow seamounts in the subtropical and tropical Eastern Atlantic, and over the adjacent abyssal plains. For the identification of food sources and trophic positions stable isotope ratios (δ13C and δ15N) were used. δ13C ranged from -24.7‰ to -15.0‰ and δ15N covered a total range of 0.9-15.9‰. Based on epipelagic particulate organic matter, zooplankton and micronekton usually occupied the 1st-3rd trophic level, including herbivorous, omnivorous and carnivorous taxa. δ13C and δ15N values were generally lower in zooplankton and micronekton of the subtropical waters as compared to the tropical region, due to the differing nutrient availability and phytoplankton communities. Correlations between δ13C and δ15N values of particulate organic matter, zooplankton, micronekton and benthopelagic fishes suggest a linear food chain based on a single energy source from primary production for Ampère Seamount, but no evidence was found for an autochthonus seamount production as compared to the open ocean reference site. Between Senghor Seamount and the open ocean δ13C signatures indicate that hydrodynamic effects at seamounts may modify the energy supply at times, but evidence for a seamount effect on the trophic structure of the pelagic communities was weak, which supports the assumption that seamount communities rely to a large extent on advected food sources.

Human baby hair amino acid natural abundance 15N-isotope values are not related to the 15N-isotope values of amino acids in mother's breast milk protein.

PubMed

Romek, Katarzyna M; Julien, Maxime; Frasquet-Darrieux, Marine; Tea, Illa; Antheaume, Ingrid; Hankard, Régis; Robins, Richard J

2013-12-01

Since exclusively breast-suckled infants obtain their nutrient only from their mother's milk, it might be anticipated that a correlation will exist between the (15)N/(14)N isotope ratios of amino acids of protein of young infants and those supplied by their mother. The work presented here aimed to determine whether amino nitrogen transfer from human milk to infant hair protein synthesized within the first month of life conserves the maternal isotopic signature or whether post-ingestion fractionation dominates the nitrogen isotope spectrum. The study was conducted at 1 month post-birth on 100 mother-infant pairs. Isotope ratios (15)N/(14)N and (13)C/(12)C were measured using isotope ratio measurement by Mass Spectrometry (irm-MS) for whole maternal milk, and infant hair and (15)N/(14)N ratios were also measured by GC-irm-MS for the N-pivaloyl-O-isopropyl esters of amino acids obtained from the hydrolysis of milk and hair proteins. The δ(15)N and δ(13)C (‰) were found to be significantly higher in infant hair than in breast milk (δ(15)N, P < 0.001; δ(13)C, P < 0.001). Furthermore, the δ(15)N (‰) of individual amino acids in infant hair was also significantly higher than that in maternal milk (P < 0.001). By calculation, the observed shift in isotope ratio was shown not to be accounted for by the amino acid composition of hair and milk proteins, indicating that it is not simply due to differences in the composition in the proteins present. Rather, it would appear that each pool-mother and infant-turns over independently, and that fractionation in infant N-metabolism even in the first month of life dominates over the nutrient N-content.

Discrimination of carbon and nitrogen isotopes from milk to serum and vibrissae in Alaska Steller sea lions (Eumetopias jubatus)

USGS Publications Warehouse

Stegall, V.K.; Farley, Sean D.; Rea, Lorrie D.; Pitcher, K.W.; Rye, R.O.; Kester, C.L.; Stricker, C.A.; Bern, C.R.

2008-01-01

Knowledge of diet-tissue stable isotope discrimination is required to properly interpret stable isotope values and to identify possible diet shifts, such as might be expected from nursing through weaning. This study compared ??13C and ??15N of paired serum and vibrissal roots with those of ingested milk (n = 52) from free-ranging Steller sea lion (Eumetopias jubatus (Schreber, 1776)) pups (1-11 months) and juveniles (14-27 months) to estimate diet-tissue discrimination. Mean 15N enrichment from ingested milk to serum was 2.1??? ?? 0.6%??? and ??15N at the root of the vibrissae (representing current growth) were not significantly different from serum values. Milk was enriched for mean 13C by 5.0??? ?? 1.0%??? and 7.3??? ?? 1.2??? relative to serum and vibrissal roots, respectively, which was due to the presence of 13C-depleted lipids in milk. This was confirmed by lipid extraction from a subset of milk and serum samples, resulting in a 5.8??? ?? 1.0??? change only in milk. This study established that vibrissal roots and serum are reflective of a milk diet with approximately 2.0??? 15N enrichment, and vibrissal roots reflect serum and lipid-extracted milk values with approximately 2.0??? 13C enrichment. These discrimination factors are important to establish for stable isotope studies assessing diet shifts. ?? 2008 NRC.

Determination of the δ15N and δ13C of total nitrogen and carbon in solids; RSIL lab code 1832

USGS Publications Warehouse

Revesz, Kinga; Qi, Haiping; Coplan, Tyler B.

2006-01-01

The purpose of the Reston Stable Isotope Laboratory (RSIL) lab code 1832 is to determine the δ(15N/14N), abbreviated as δ15N, and the δ(13C/12C), abbreviated as δ13C, of total nitrogen and carbon in a solid sample. A Carlo Erba NC 2500 elemental analyzer (EA) is used to convert total nitrogen and carbon in a solid sample into N2 and CO2 gas. The EA is connected to a continuous flow isotope-ratio mass spectrometer (CF-IRMS), which determines the relative difference in stable nitrogen isotope-amount ratio (15N/14N) of the product N2 gas and the relative difference in stable carbon isotope-amount ratio (13C/12C) of the product CO2 gas. The combustion is quantitative; no isotopic fractionation is involved. Samples are placed in tin capsules and loaded into a Costech Zero Blank Autosampler on the EA. Under computer control, samples then are dropped into a heated reaction tube that contains an oxidant, where combustion takes place in a helium atmosphere containing an excess of oxygen gas. Combustion products are transported by a helium carrier through a reduction furnace to remove excess oxygen and to convert all nitrous oxides into N2 and through a drying tube to remove water. The gas-phase products, mainly CO2 and N2, are separated by a gas chromatograph. The gas is then introduced into the IRMS through a Finnigan MAT (now Thermo Scientific) ConFlo II interface. The Finnigan MAT ConFlo II interface is used for introducing not only sample into the IRMS but also N2 and CO2 reference gases and helium for sample dilution. The flash combustion is quantitative; no isotopic fractionation is involved. The IRMS is a Thermo Scientific Delta V CF-IRMS. It has a universal triple collector, two wide cups with a narrow cup in the middle; it is capable of measuring mass/charge (m/z) 28, 29, 30 or with a magnet current change 44, 45, 46, simultaneously. The ion beams from these m/z values are as follows: m/z 28 = N2 = 14N/14N; m/z 29 = N2 = 14N/15N primarily; m/z 30 = NO = 14N/16O primarily, which is a sign of contamination or incomplete reduction; m/z 44 = CO2 = 12C16O16O; m/z 45 = CO2 = 13C16O16O primarily; and m/z 46 = CO2 = 12C16O18O primarily.

Freezing and fractionation: effects of preservation on carbon and nitrogen stable isotope ratios of some limnetic organisms.

PubMed

Wolf, J Marshall; Johnson, Brett; Silver, Douglas; Pate, William; Christianson, Kyle

2016-03-15

Stable isotopes of carbon and nitrogen have become important natural tracers for studying food-web structure and function. Considerable research has demonstrated that chemical preservatives and fixatives shift the isotopic ratios of aquatic organisms. Much less is known about the effects of freezing as a preservation method although this technique is commonly used. We conducted a controlled experiment to test the effects of freezing (-10 °C) and flash freezing (–79 °C) on the carbon and nitrogen isotope ratios of zooplankton (Cladocera), Mysis diluviana and Rainbow Trout (Oncorhynchus mykiss). Subsamples (~0.5 mg) of dried material were analyzed for percentage carbon, percentage nitrogen, and the relative abundance of stable carbon and nitrogen isotopes (δ13C and δ15N values) using a Carlo Erba NC2500 elemental analyzer interfaced to a ThermoFinnigan MAT Delta Plus isotope ratio mass spectrometer. The effects of freezing were taxon-dependent. Freezing had no effect on the isotopic or elemental values of Rainbow Trout muscle. Effects on the δ13C and δ15N values of zooplankton and Mysis were statistically significant but small relative to typical values of trophic fractionation. The treatment-control offsets had larger absolute values for Mysis (δ13C: ≤0.76 ± 0.41‰, δ15N: ≤0.37 ± 0.16‰) than for zooplankton (δ13C: ≤0.12 ± 0.06‰, δ15N: ≤0.30 ± 0.27‰). The effects of freezing were more variable for the δ13C values of Mysis, and more variable for the δ15N values of zooplankton. Generally, both freezing methods reduced the carbon content of zooplankton and Mysis, but freezing had a negative effect on the %N of zooplankton and a positive effect on the %N of Mysis. The species-dependencies and variability of freezing effects on aquatic organisms suggest that more research is needed to understand the mechanisms responsible for freezing-related fractionation before standardized protocols for freezing as a preservation method can be adopted.

Stable isotopes to discriminate lambs fed herbage or concentrate both obtained from C(3) plants.

PubMed

Moreno-Rojas, Jose M; Vasta, Valentina; Lanza, Alfio; Luciano, Giuseppe; Ladroue, Virginie; Guillou, Claude; Priolo, Alessandro

2008-12-01

This study was aimed at determining whether isotopic ratio mass spectrometry (IRMS) enables us to discriminate between lambs fed herbage or concentrate, both obtained from C(3) plants, and those fed a concentrate obtained from C(4) plants. Thirty-four Comisana male lambs (age 45 days) were assigned to three feeding treatments. Fourteen lambs were fed vetch (Vicia sativa) ad libitum. Another fourteen lambs received a barley-based concentrate. The remaining six lambs were fed a maize-based concentrate. After 60 days of experimental treatment the animals were slaughtered and the wool, perirenal fat and muscle longissimus dorsi were sampled. The delta(13)C and delta(15)N values of the muscle, wool and feed were measured by continuous flow elemental analysis (CF-EA)-IRMS. The delta(13)C of the fat was determined likewise. The isotopic composition of the tissues reflected that of the three diets. For the lambs which were fed herbage the muscle delta(13)C values were higher (P < 0.0005) and delta(15)N values were lower (P < 0.0005) than those of the lambs receiving concentrates. The delta(15)N and delta(13)C values in the muscle and delta(13)C values in the adipose tissue allowed perfect discrimination between the lambs fed the three different diets. The regression between the delta(13)C values measured in muscle and in wool of lambs was linear (R(2) = 0.99; P < 0.0005). This result shows that delta(13)C measured in the wool can predict muscle delta(13)C distribution, suggesting that wool is a valuable matrix for meat authentication.

The molecular core in G34.3 + 0.2 - Millimeter interferometric observations of HCO(+), H(C-13)N, H(C-15)N, and SO

NASA Technical Reports Server (NTRS)

Carral, Patricia; Welch, William J.

1992-01-01

This study presents high-resolution observations of the molecular core in the star-forming region G34.3 + 0.2. Maps at 6-arcsec resolution of emission and absorption of the J = 1 - 0 transitions of HCO(+), H (C-13)N, H(C-15)N, and of the 2(2) - 1(1) transition of SO were obtained in addition to a map of the 3.4-mm continuum emission from the compact H II component. The HCL(+) emission toward G34.3 + 0.2 traces a warm molecular core about 0.9 pc in size. Emission from H (C-13)N is detected over about 0.3 pc. The cometary H II region lies near the edge of the molecular core. The blueshift of the radio recombination lines with respect to the molecular emission suggests that gas from the H II region is accelerated in a champagne flow caused by a steep gradient in the ambient gas density.

Observations of nitrogen isotope fractionation in deeply embedded protostars

NASA Astrophysics Data System (ADS)

Wampfler, S. F.; Jørgensen, J. K.; Bizzarro, M.; Bisschop, S. E.

2014-12-01

Context. The terrestrial planets, comets, and meteorites are significantly enriched in 15N compared to the Sun and Jupiter. While the solar and jovian nitrogen isotope ratio is believed to represent the composition of the protosolar nebula, a still unidentified process has caused 15N-enrichment in the solids. Several mechanisms have been proposed to explain the variations, including chemical fractionation. However, observational results that constrain the fractionation models are scarce. While there is evidence of 15N-enrichment in prestellar cores, it is unclear how the signature evolves into the protostellar phases. Aims: The aim of this study is to measure the 14N/15N ratio around three nearby, embedded low- to intermediate-mass protostars. Methods: Isotopologues of HCN and HNC were used to probe the 14N/15N ratio. A selection of J = 3-2 and 4-3 transitions of H13CN, HC15N, HN13C, and H15NC was observed with the Atacama Pathfinder EXperiment telescope (APEX). The 14N/15N ratios were derived from the integrated intensities assuming a standard 12C/13C ratio. The assumption of optically thin emission was verified using radiative transfer modeling and hyperfine structure fitting. Results: Two sources, IRAS 16293A and R CrA IRS7B, show 15N-enrichment by a factor of ~1.5-2.5 in both HCN and HNC with respect to the solar composition. IRAS 16293A falls in the range of typical prestellar core values. Solar composition cannot be excluded for the third source, OMC-3 MMS6. Furthermore, there are indications of a trend toward increasing 14N/15N ratios with increasing outer envelope temperature. Conclusions: The enhanced 15N abundances in HCN and HNC found in two Class 0 sources (14N /15N ~ 160-290) and the tentative trend toward a temperature-dependent 14N/15N ratio are consistent with the chemical fractionation scenario, but 14N/15N ratios from additional tracers are indispensable for testing the models. Spatially resolved observations are needed to distinguish between chemical fractionation and isotope-selective photochemistry. Appendices are available in electronic form at http://www.aanda.org

Isotopic evidence indicates saprotrophy in post-fire Morchella in Oregon and Alaska.

PubMed

Hobbie, Erik A; Rice, Samuel F; Weber, Nancy S; Smith, Jane E

2016-01-01

We assessed the nutritional strategy of true morels (genus Morchella) collected in 2003 and 2004 in Oregon and Alaska, 1 or 2 y after forest fires. We hypothesized that the patterns of stable isotopes (δ(13)C and δ(15)N) in the sporocarps would match those of saprotrophic fungi and that radiocarbon (Δ(14)C) analyses would indicate that Morchella was assimilating old carbon not current-year photosynthate. We compared radiocarbon and stable isotopes in Morchella with values from concurrently collected foliage, the ectomycorrhizal Geopyxis carbonaria (Alb. & Schwein.) Sacc., the saprotrophic Plicaria endocarpoides (Berk.) Rifai, and with literature to determine isotopic values for ectomycorrhizal or saprotrophic fungi. Geopyxis, Plicaria and Morchella, respectively, were 3‰, 5‰ and 6‰ higher in 13C than foliage and 5‰, 7‰ and 7‰ higher in (15)N. High (15)N enrichment in Morchella indicated that recent litter was not the primary source for Morchella nitrogen, and similar (13)C and (15)N enrichments to Plicaria suggest that Morchella assimilates its carbon and nitrogen from the same source pool as this saprotrophic fungus. From radiocarbon analyses Morchella averaged 11 ± 6 y old (n = 19), Plicaria averaged 17 ± 5 y old (n = 3), foliage averaged 1 ± 2 y old (n = 8) and Geopyxis (n = 1) resembled foliage in Δ(14)C. We conclude that morels fruiting in post-fire environments in our study assimilated old carbon and were saprotrophic. © 2016 by The Mycological Society of America.

Stable isotope ratios and mercury levels in red meat products from baleen whales sold in Japanese markets.

PubMed

Endo, Tetsuya; Hotta, Yohei; Hisamichi, Yohsuke; Kimura, Osamu; Sato, Rie; Haraguchi, Koichi; Funahashi, Naoko; Baker, C Scott

2012-05-01

We analyzed the δ(13)C, δ(15)N and δ(18)O values and Hg concentration in red meat products originating from the predominant types sold in Japan for human consumption: two populations of common minke (J- and O-types), Bryde's and sei whales in the western North Pacific Ocean, and fin and Antarctic minke whales in the Southern Ocean. The order of the trophic positions, evaluated by δ(15)N values and Hg concentrations, coincided with their known feeding habits: common minke (J-type)=common minke (O-type)> Bryde's ≥ sei ≥ Antarctic minke ≥ fin. The Hg concentrations in the combined samples from the six samples were significantly correlated with their δ(15)N values (γ=0.455, n=66, p<0.05), reflecting overall differences in the trophic level. This correlation was not significant for within-species comparison for the common minke (J- and O-types) or the Bryde's whale, probably reflecting the higher δ(15)N value and lower Hg concentration in the North Pacific Ocean around Japan. Determination of δ(13)C, δ(15)N and δ(18)O could be used to discriminate between the red meat products originating from the whale species in the North Pacific and Southern Oceans. However, the four whale species or populations in the Pacific Ocean could not be discriminated on basis of these values, nor could the two species in the Southern Ocean. Positive correlations between the δ(13)C and δ(15)N values and negative correlations between the δ(15)N and δ(18)O values and the δ(13)C and δ(18)O values, probably reflecting migration patterns, were found in some whale species in the North Pacific and Southern Oceans. Copyright © 2012 Elsevier Inc. All rights reserved.

Distribution and source of organic matter in surface sediment from the muddy deposit along the Zhejiang coast, East China Sea.

PubMed

Xu, Gang; Liu, Jian; Hu, Gang; Jonell, Tara N; Chen, Lilei

2017-10-15

To constrain organic matter compositions and origins, elemental (TOC, TN, C/N) and stable carbon (δ 13 C) and nitrogen isotope (δ 15 N) compositions are measured for surface sediments collected from muddy deposit along the Zhejiang coast, East China Sea. The results showed that the TOC, TN, C/N, δ 13 C, and δ 15 N were 0.19-0.67%, 0.03-0.09%, 6.76-9.22, -23.43 to -20.26‰, and 3.93-5.27‰, respectively. The δ 13 C values showed that the mixing inputs of terrigenous and marine organic matter generally dominated sedimentary organic matter in the west part, and the sedimentary organic matters were mainly influenced by the marine organic matter in the east part of the study area. A stable carbon isotope two end member mixing model estimates ~38% terrestrial -derived and ~62% marine-derived inputs to sedimentary organic matter. Microbial mineralization strongly controls δ 15 N values, and therefore cannot be used to identify the provenance of organic matter for the Zhenjiang coast. Copyright © 2017. Published by Elsevier Ltd.

Stable isotope discrimination factors and between-tissue isotope comparisons for bone and skin from captive and wild green sea turtles (Chelonia mydas).

PubMed

Turner Tomaszewicz, Calandra N; Seminoff, Jeffrey A; Price, Mike; Kurle, Carolyn M

2017-11-30

The ecological application of stable isotope analysis (SIA) relies on taxa- and tissue-specific stable carbon (Δ 13 C) and nitrogen (Δ 15 N) isotope discrimination factors, determined with captive animals reared on known diets for sufficient time to reflect dietary isotope ratios. However, captive studies often prohibit lethal sampling, are difficult with endangered species, and reflect conditions not experienced in the wild. We overcame these constraints and determined the Δ 13 C and Δ 15 N values for skin and cortical bone from green sea turtles (Chelonia mydas) that died in captivity and evaluated the utility of a mathematical approach to predict discrimination factors. Using stable carbon (δ 13 C values) and nitrogen (δ 15 N values) isotope ratios from captive and wild turtles, we established relationships between bone stable isotope (SI) ratios and those from skin, a non-lethally sampled tissue, to facilitate comparisons of SI ratios among studies using multiple tissues. The mean (±SD) Δ 13 C and Δ 15 N values (‰) between skin and bone from captive turtles and their diet (non-lipid-extracted) were 2.3 ± 0.3 and 4.1 ± 0.4 and 2.1 ± 0.6 and 5.1 ± 1.1, respectively. The mathematically predicted Δ 13 C and Δ 15 N values were similar (to within 1‰) to the experimentally derived values. The mean δ 15 N values from bone were higher than those from skin for captive (+1.0 ± 0.9‰) and wild (+0.8 ± 1.0‰) turtles; the mean δ 13 C values from bone were lower than those from skin for wild turtles (-0.6 ± 0.9‰), but the same as for captive turtles. We used linear regression equations to describe bone vs skin relationships and create bone-to-skin isotope conversion equations. For sea turtles, we provide the first (a) bone-diet SI discrimination factors, (b) comparison of SI ratios from individual-specific bone and skin, and (c) evaluation of the application of a mathematical approach to predict stable isotope discrimination factors. Our approach opens the door for future studies comparing different tissues, and relating SI ratios of captive to wild animals. Copyright © 2017 John Wiley & Sons, Ltd.

Effect of lipid extraction on analyses of stable carbon and stable nitrogen isotopes in coastal organisms of the Aleutian archipelago

USGS Publications Warehouse

Ricca, M.A.; Miles, A.K.; Anthony, R.G.; Deng, X.; Hung, S.S.O.

2007-01-01

We tested whether extracting lipids reduced confounding variation in ??13C and ??15N values by analyzing paired lipid-extracted (LE) and non-lipid-extracted (NLE) samples of bald eagle (Haliaeetus leucocephalus (L., 1766)) whole eggs, muscle tissue from nine seabird and one terrestrial bird species, muscle tissue from four marine fish species, and blue mussels (Mytilus edulis L., 1758) collected from the Aleutian archipelago, Alaska. Lipid extraction significantly increased ??13C by an average of 2.0??? in whole eggs, 0.8??? in avian muscle, 0.2??? in fish muscle, and 0.6??? in blue mussels. Lower ??13C values in NLE samples covaried positively with lipid content across all sample types. Lower ??13C values in NLE samples were not correlated with lipid content within bald eagle eggs and blue mussels, but covaried positively with percent lipid in avian and fish muscles. Neither lipid extraction nor percent lipid significantly changed ??15N values for any sample type. Lower ??13C values in most NLE avian and fish muscle tissues should not confound interpretation of pelagic versus nearshore sources of primary production, but lipid extraction may be necessary when highly precise estimates of ??13C are needed. Lipid extraction may not be necessary when only ??15N is of interest. ?? 2007 NRC.

HN(α/β-COCA-J) Experiment for Measurement of 1JC‧Cα Couplings from Two-Dimensional [15N, 1H] Correlation Spectrum

NASA Astrophysics Data System (ADS)

Permi, Perttu; Sorsa, Tia; Kilpeläinen, Ilkka; Annila, Arto

1999-11-01

Anew method for measurement of one-bond 13C‧-13Cα scalar and dipolar couplings from a two-dimensional [15N, 1H] correlation spectrum is presented. The experiment is based on multiple-quantum coherence, which is created between nitrogen and carbonyl carbon for simultaneous evolution of 15N chemical shift and coupling between 13C‧ and 13Cα. Optional subspectral editing is provided by the spin-state-selective filters. The residual dipolar dipolar contribution to the 13C‧-13Cα coupling can be measured from these simplified [15N, 1H]-HSQC-like spectra. In this way, without explicit knowledge of carbon assignments, conformational changes of proteins dissolved in dilute liquid crystals can be probed conveniently, e.g., in structure activity relationship by NMR studies. The method is demonstrated with human cardiac troponin C.

Alternative SAIL-Trp for robust aromatic signal assignment and determination of the χ(2) conformation by intra-residue NOEs.

PubMed

Miyanoiri, Yohei; Takeda, Mitsuhiro; Jee, JunGoo; Ono, Akira M; Okuma, Kosuke; Terauchi, Tsutomu; Kainosho, Masatsune

2011-12-01

Tryptophan (Trp) residues are frequently found in the hydrophobic cores of proteins, and therefore, their side-chain conformations, especially the precise locations of the bulky indole rings, are critical for determining structures by NMR. However, when analyzing [U-(13)C,(15)N]-proteins, the observation and assignment of the ring signals are often hampered by excessive overlaps and tight spin couplings. These difficulties have been greatly alleviated by using stereo-array isotope labeled (SAIL) proteins, which are composed of isotope-labeled amino acids optimized for unambiguous side-chain NMR assignment, exclusively through the (13)C-(13)C and (13)C-(1)H spin coupling networks (Kainosho et al. in Nature 440:52-57, 2006). In this paper, we propose an alternative type of SAIL-Trp with the [ζ2,ζ3-(2)H(2); δ1,ε3,η2-(13)C(3); ε1-(15)N]-indole ring ([(12)C (γ,) ( 12) C(ε2)] SAIL-Trp), which provides a more robust way to correlate the (1)H(β), (1)H(α), and (1)H(N) to the (1)H(δ1) and (1)H(ε3) through the intra-residue NOEs. The assignment of the (1)H(δ1)/(13)C(δ1) and (1)H(ε3)/(13)C(ε3) signals can thus be transferred to the (1)H(ε1)/(15)N(ε1) and (1)H(η2)/(13)C(η2) signals, as with the previous type of SAIL-Trp, which has an extra (13)C at the C(γ) of the ring. By taking advantage of the stereospecific deuteration of one of the prochiral β-methylene protons, which was (1)H(β2) in this experiment, one can determine the side-chain conformation of the Trp residue including the χ(2) angle, which is especially important for Trp residues, as they can adopt three preferred conformations. We demonstrated the usefulness of [(12)C(γ),(12)C(ε2)] SAIL-Trp for the 12 kDa DNA binding domain of mouse c-Myb protein (Myb-R2R3), which contains six Trp residues.

Bioaccumulation and biomagnification of mercury and methylmercury in four sympatric coastal sharks in a protected subtropical lagoon.

PubMed

Matulik, Adam G; Kerstetter, David W; Hammerschlag, Neil; Divoll, Timothy; Hammerschmidt, Chad R; Evers, David C

2017-03-15

Mercury bioaccumulation is frequently observed in marine ecosystems, often with stronger effects at higher trophic levels. We compared total mercury (THg) and methylmercury (MeHg) from muscle with length, comparative isotopic niche, and diet (via δ 13 C and δ 15 N) among four sympatric coastal sharks in Florida Bay (USA): blacknose, blacktip, bull, and lemon. Mercury in blacknose and blacktip sharks increased significantly with size, whereas bull and lemon sharks had a high variance in mercury relative to size. Both δ 13 C and δ 15 N were consistent with general resource use and trophic position relationships across all species. A significant relationship was observed between δ 13 C and mercury in blacktip sharks, suggesting an ontogenetic shift isotopic niche, possibly a dietary change. Multiple regression showed that δ 13 C and δ 15 N were the strongest factors regarding mercury bioaccumulation in individuals across all species. Additional research is recommended to resolve the mechanisms that determine mercury biomagnification in individual shark species. Copyright © 2017 Elsevier Ltd. All rights reserved.

(15)N and (13)C group-selective techniques extend the scope of STD NMR detection of weak host-guest interactions and ligand screening.

PubMed

Kövér, Katalin E; Wéber, Edit; Martinek, Tamás A; Monostori, Eva; Batta, Gyula

2010-10-18

Saturation transfer difference (STD) is a valuable tool for studying the binding of small molecules to large biomolecules and for obtaining detailed information on the binding epitopes. Here, we demonstrate that the proposed (15)N/(13)C variants of group-selective, "GS-STD" experiments provide a powerful approach to mapping the binding epitope of a ligand even in the absence of efficient spin diffusion within the target protein. Therefore, these experimental variants broaden the scope of STD studies to smaller and/or more-dynamic targets. The STD spectra obtained in four different experimental setups (selective (1)H STD, (15)N GS-STD, (13)C(Ar) and (13)C(aliphatic) GS-STD approaches) revealed that the signal-intensity pattern of the difference spectra is affected by both the type and the spatial distribution of the excited "transmitter" atoms, as well as by the efficiency of the spin-diffusion-mediated magnetization transfer. The performance of the experiments is demonstrated on a system by using the lectin, galectin-1 and its carbohydrate ligand, lactose.

13C and 15N fractionation of CH4/N2 mixtures during photochemical aerosol formation: Relevance to Titan

NASA Astrophysics Data System (ADS)

Sebree, Joshua A.; Stern, Jennifer C.; Mandt, Kathleen E.; Domagal-Goldman, Shawn D.; Trainer, Melissa G.

2016-05-01

The ratios of the stable isotopes that comprise each chemical species in Titan's atmosphere provide critical information towards understanding the processes taking place within its modern and ancient atmosphere. Several stable isotope pairs, including 12C/13C and 14N/15N, have been measured in situ or probed spectroscopically by Cassini-borne instruments, space telescopes, or through ground-based observations. Current attempts to model the observed isotope ratios incorporate fractionation resulting from atmospheric diffusion, hydrodynamic escape, and primary photochemical processes. However, the effect of a potentially critical pathway for isotopic fractionation - organic aerosol formation and subsequent deposition onto the surface of Titan - has not been considered due to insufficient data regarding fractionation during aerosol formation. To better understand the nature of this process, we have conducted a laboratory study to measure the isotopic fractionation associated with the formation of Titan aerosol analogs, commonly referred to as 'tholins', via far-UV irradiation of several methane (CH4) and dinitrogen (N2) mixtures. Analysis of the δ13C and δ15N isotopic signatures of the photochemical aerosol products using an isotope ratio mass spectrometer (IRMS) show that fractionation direction and magnitude are dependent on the initial bulk composition of the gas mixture. In general, the aerosols showed enrichment in 13C and 14N, and the observed fractionation trends can provide insight into the chemical mechanisms controlling photochemical aerosol formation.

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

PubMed

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

2004-11-01

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

NMR 1H,13C, 15N backbone and 13C side chain resonance assignment of the G12C mutant of human K-Ras bound to GDP.

PubMed

Sharma, Alok K; Lee, Seung-Joo; Rigby, Alan C; Townson, Sharon A

2018-05-02

K-Ras is a key driver of oncogenesis, accounting for approximately 80% of Ras-driven human cancers. The small GTPase cycles between an inactive, GDP-bound and an active, GTP-bound state, regulated by guanine nucleotide exchange factors and GTPase activating proteins, respectively. Activated K-Ras regulates cell proliferation, differentiation and survival by signaling through several effector pathways, including Raf-MAPK. Oncogenic mutations that impair the GTPase activity of K-Ras result in a hyperactivated state, leading to uncontrolled cellular proliferation and tumorogenesis. A cysteine mutation at glycine 12 is commonly found in K-Ras associated cancers, and has become a recent focus for therapeutic intervention. We report here 1 H N, 15 N, and 13 C resonance assignments for the 19.3 kDa (aa 1-169) human K-Ras protein harboring an oncogenic G12C mutation in the GDP-bound form (K-RAS G12C-GDP ), using heteronuclear, multidimensional NMR spectroscopy. Backbone 1 H- 15 N correlations have been assigned for all non-proline residues, except for the first methionine residue.

Abundances in red giant stars - Nitrogen isotopes in carbon-rich molecular envelopes

NASA Technical Reports Server (NTRS)

Wannier, P. G.; Andersson, B.-G.; Olofsson, H.; Ukita, N.; Young, K.

1991-01-01

Results are presented of millimeter- and submillimeter-wave observations of HCN and HCCCN that were made of the circmustellar envelopes of eight carbon stars, including the two protoplanetary nebulae CRL 618 and CRL 2688. The observations yield a measure of the double ratio (N-14)(C-13)/(N-15)(C-12). Measured C-12/C-13 ratios are used to estimate the N-14/N-15 abundance ratio, with the resulting lower limits in all eight envelopes and possible direct determinations in two envelopes. The two determinations and four of the remaining six lower limits are found to be in excess of the terrestrial value of N-14/N-15 = 272, indicating an evolution of the nitrogen isotope ratio, which is consistent with stellar CNO processing. Observations of thermal SiO (v = 0, J = 2-1) emission show that the Si-29/Si-28 ratio can be determined in carbon stars, and further observations are indicated.

Buckley ANGB, Aurora, Colorado. Revised Uniform Summary of Surface Weather Observations (RUSSWO). Parts A-F

DTIC Science & Technology

1981-02-18

OSURATIKM) 23036 bUCALEY ANG8 Qb-7.37 SYATIALL WATHER ’. 2100-2300 6LASO Nouni IINYS15) 1.3 446 ?-to 11.16 17-1 21 .3V 3.33 34.46 41.0 4.33t 1116 WOW N . 19...bulb 3398619 561 6 0ol 2,63? 930 ,. 1 1 t,% 193720m~nK( �.44.9 810 3 I I z ~ -- - -. - - I I A U GSAFETAC PSYCHROMETRIC SUMMARY AIR WATHER

6-Aminopenicillanic acid revisited: A combined solid state NMR and in silico refinement

NASA Astrophysics Data System (ADS)

Aguiar, Daniel Lima Marques de; San Gil, Rosane Aguiar da Silva; Alencastro, Ricardo Bicca de; Souza, Eugenio Furtado de; Borré, Leandro Bandeira; Vaiss, Viviane da Silva; Leitão, Alexandre Amaral

2016-09-01

13C/15N (experimental and ab initio) solid-state NMR was used to achieve an affordable way to improve hydrogen refinement of 6-aminopenicillanic acid (6-APA) structure. The lattice effect on the isotropic chemical shifts was probed by using two different magnetic shielding calculations: isolated molecules and periodic crystal structure. The electron density difference maps of optimized and non-optimized structures were calculated in order to investigate the interactions inside the 6-APA unit cell. The 13C and 15N chemical shifts assignments were unambiguously stablished. In addition, some of the literature 13C resonances ambiguities could be properly solved.

Plasticity of trophic interactions among sharks from the oceanic south-western Indian Ocean revealed by stable isotope and mercury analyses

NASA Astrophysics Data System (ADS)

Kiszka, Jeremy J.; Aubail, Aurore; Hussey, Nigel E.; Heithaus, Michael R.; Caurant, Florence; Bustamante, Paco

2015-02-01

Sharks are a major component of the top predator guild in oceanic ecosystems, but the trophic relationships of many populations remain poorly understood. We examined chemical tracers of diet and habitat (δ15N and δ13C, respectively) and total mercury (Hg) concentrations in muscle tissue of seven pelagic sharks: blue shark (Prionace glauca), short-fin mako shark (Isurus oxyrinchus), oceanic whitetip shark (Carcharhinus longimanus), scalloped hammerhead shark (Sphyrna lewini), pelagic thresher shark (Alopias pelagicus), crocodile shark (Pseudocarcharias kamoharai) and silky shark (Carcharhinus falciformis), from the data poor south-western tropical Indian Ocean. Minimal interspecific variation in mean δ15N values and a large degree of isotopic niche overlap - driven by high intraspecific variation in δ15N values - was observed among pelagic sharks. Similarly, δ13C values of sharks overlapped considerably for all species with the exception of P. glauca, which had more 13C-depleted values indicating possibly longer residence times in purely pelagic waters. Geographic variation in δ13C, δ15N and Hg were observed for P. glauca and I. oxyrinchus. Mean Hg levels were similar among species with the exception of P. kamoharai which had significantly higher Hg concentrations likely related to mesopelagic feeding. Hg concentrations increased with body size in I. oxyrinchus, P. glauca and C. longimanus. Values of δ15N and δ13C varied with size only in P. glauca, suggesting ontogenetic shifts in diets or habitats. Together, isotopic data indicate that - with few exceptions - variance within species in trophic interactions or foraging habitats is greater than differentiation among pelagic sharks in the south-western Indian Ocean. Therefore, it is possible that this group exhibits some level of trophic redundancy, but further studies of diets and fine-scale habitat use are needed to fully test this hypothesis.

15N and13C NMR investigation of hydroxylamine-derivatized humic substances

USGS Publications Warehouse

Thorn, K.A.; Arterburn, J.B.; Mikita, M.A.

1992-01-01

Five fulvic and humic acid samples of diverse origins were derivatized with 15N-labeled hydroxylamine and analyzed by liquid-phase 15N NMR spectrometry. The 15N NMR spectra indicated that hydroxylamine reacted similarly with all samples and could discriminate among carbonyl functional groups. Oximes were the major derivatives; resonances attributable to hydroxamic acids, the reaction products of hydroxylamine with esters, and resonances attributable to the tautomeric equilibrium position between the nitrosophenol and monoxime derivatives of quinones, the first direct spectroscopic evidence for quinones, also were evident. The 15N NMR spectra also suggested the presence of nitriles, oxazoles, oxazolines, isocyanides, amides, and lactams, which may all be explained in terms of Beckmann reactions of the initial oxime derivatives. INEPT and ACOUSTIC 15N NMR spectra provided complementary information on the derivatized samples. 13C NMR spectra of derivatized samples indicated that the ketone/quinone functionality is incompletely derivatized with hydroxylamine. ?? 1991 American Chemical Society.

Investigating trophic relationships of pinnipeds in Alaska and Washington using stable isotope ratios of nitrogen and carbon

USGS Publications Warehouse

Hobson, Keith A.; Sease, John L.; Merrick, Richard L.; Piatt, John F.

1997-01-01

We measured stable-nitrogen (δ15N) and stable-carbon (δ13C) isotope ratios in muscle and hair from 7 northern fur seals (Callorhinus ursinus) from the Pribilof Islands, Alaska, and 27 Steller sea lions (Eumetopias jubatus), and 14 harbor seals (Phoca vitulina) from the Gulf of Alaska and coast of Washington State, in order to contrast dietary information derived from isotopic vs. available conventional dietary studies. Stable-nitrogen-isotope analysis of muscle revealed that harbor seals were enriched over sea lions (mean δ15N = 18.6‰vs. 17.5‰) which were in turn enriched over northern fur seals (mean δ15N = 16.6‰). Trophic segregation among these species likely results primarily from differential reliance on herring (Clupea harengus), Atka mackerel (Pleurogrammus monopterygius), and large vs. small walleye pollock (Theregra chalcogramma). According to their δ15N values, adult male Steller sea lions showed a higher trophic position than adult females (mean δ15N: 18.0‰ vs. 17.2‰), whereas adult female northern fur seals were trophically higher than juvenile male fur seals (mean δ15N: 16.5‰vs. 15.0‰). Each of these observed differences likely resulted from differential reliance on squid or differences in the size range of pollock consumed. Three northern fur seal pups showed higher δ15N enrichment over adults (mean 17.7‰vs. 15.8‰) due to their reliance on their mother's milk. Stable-carbon isotope measurements of hair revealed a cline toward more negative values with latitude. Segregation in hair δ13C between Steller sea lions and harbor seals off the coast of Washington (mean δ13C: -13.6‰ vs. -15.0‰) reflected the greater association of harbor seals with freshwater input from the Columbia River. Our study demonstrates the utility of the stable isotope approach to augment conventional dietary analyses of pinnipeds and other marine mammals.

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

NASA Astrophysics Data System (ADS)

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

2014-05-01

Soil organic matter (SOM) contains three times more carbon than in the atmosphere or terrestrial vegetation. This major pool of organic carbon is sensitive to climate change, but the mechanisms for carbon stabilization in soils are still not well understood and the ultimate potential for carbon stabilization is unknown. For predicting SOM dynamics, it is necessary to gain information on the turnover rates or stability of different soil organic carbon pools. The common method to determine stability and age of SOM is the 14C radio carbon technique, which is very expensive and therefore limited in use. Conen et al. (2008) developed a model to estimate the SOM stability based on the isotopic discrimination of 15N natural abundance by soil micro-organisms, and the decreasing C:N ratio during organic matter decomposition. This model has been developed for permanent grasslands in the Swiss Alps under steady-state conditions. The objective of our study was to validate whether this model could be used or adapted, in combination with 13C isotope signatures of SOM, to predict the relative age and stability of SOM fractions in more disturbed agricultural ecosystems. The present study was carried out on soils collected from six long-term experimental trials (from 12 to 50 years) under different agricultural management practices (e.g. no tillage vs conventional tillage, and mulch, fertilizer, green or animal manure application), located in Austria, Belgium, Kenya and China. Top and subsoil were sampled until 80-100 cm depth. Particulate organic matter (POM) fraction was obtained by wet sieving (> 63μm) after sonification and density separation (<1.8 g cm-3). Carbon and nitrogen contents and their stable isotopic ratios (i.e. 15N and 13C) were measured in POM and bulk soils. The mineral associated matter fraction (mOM), as the protected carbon, was calculated by difference to the bulk soil organic carbon. The relative age of the SOM was calculated using the Conen model and preliminary validated by 14C dating. At all sites, the POM has a higher C:N ratio and a lower δ15N signature compared to the mOM fraction. The POM in top soil layers (<30 cm) has a lower C:N ratio than in deep soil. The C:N ratio and δ15N of POM was influenced by agricultural management. The mOM fraction has 53 to 2063 times longer turnover rate than POM, the relative age of the SOM raised with increasing soil depth. The combination of the above results with δ13C data lead to a more comprehensive understanding of the processes underlying SOM dynamics. Tillage practices increased the bulk δ13C signature of the SOM in the deeper subsoil, suggesting the presence of more stable decomposed materials. The results of this research seem to indicate that the model, developed for grasslands, can be used to determine the stability of SOM in agricultural ecosystems. The C:N ratio and δ15N signature of the POM and mOM fraction follow the expected model pattern. The isotopic δ13C signature can further enhance the understanding of the processes driving SOM stability.

High variability in spatial and temporal size-based trophodynamics of deep-sea fishes from the Mid-Atlantic Ridge elucidated by stable isotopes

NASA Astrophysics Data System (ADS)

Reid, William D. K.; Sweeting, Christopher J.; Wigham, Ben D.; McGill, Rona A. R.; Polunin, Nicholas V. C.

2013-12-01

Demersal fish play an important role in the deep-sea ecosystem by acting as a link to mobile food in the water column, consuming benthic fauna, breaking down large food parcels and dispersing organic matter over large areas. Poor diet resolution from stomach content analysis often impairs the ability to assess differences in inter- and intra-population trophodynamics and therefore understand resource partitioning among deep-sea fishes. Antimora rostrata (predator-scavenger), Coryphaenoides armatus (predator-scavenger), Coryphaenoides brevibarbis (predator) and Halosauropsis macrochir (predator) were collected from 3 stations on the Mid-Atlantic Ridge (MAR) in 2007 and 2009 to investigate trophic ecology using δ13C and δ15N. Variability in lipid-normalised δ13C (δ13Cn) and δ15N was explained by body length in all species but slope and significance of the isotope-length relationships varied both temporally and spatially. δ15N increases with length were observed in A. rostrata at all stations, C. brevibarbis and H. macrochir at one or more stations but were absent in C. armatus. δ13Cn increased with length in A. rostrata but the slope of δ13Cn-length relationships varied spatially and temporally in C. armatus and C. brevibarbis. The co-occurring δ13Cn and δ15N size-based trends in A. rostrata and H. macrochir suggested that size-based trends were a result of increasing trophic position. In C. armatus and C. brevibarbis the isotope-length trends were difficult to distinguish among trophic position increases, shifts in resource use i.e. benthic to pelagic or internal physiology. However, the overall strength, direction and significance of isotope-length trends varied temporally and spatially which suggested varying degrees of overlap in trophic ecology and feeding plasticity among these species.

Rigid, Perfectly Plastic Analysis of Ring-Stiffened Shells Under Dynamic Loading

DTIC Science & Technology

1986-08-01

Elastic-Viscoplastic Response of Clamped Beams Under Uniformly Distributed Impulse, Technical Report AFML-TR-68-396, Jan 1969. 15. Save , M. A. and...Edition, 1959, pp. 466-471 (Chapter 15). A-4. Save , M. A. and Massonnett, C. E., Plastic Analysis and Design of Plates, Shells, and Discs, North-Holland...TYPE TYESHORT (2 ɞ) HIGH LOAnD p > I + CONDITIONS u C 2 (-1) 0 T 1 0 x < MOMENT m Ix, T) 2 +1 OR -RESULTANT Lxo u.=-g- MEMBRANE n,= RESULTANT

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 between infected and parasite-free individuals. These results contribute to our understanding of data obtained from field and commercial hatcheries; and strongly improve the applicability of the stable isotope method in understanding life-history and trophic ecology of fish populations.

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 between infected and parasite-free individuals. These results contribute to our understanding of data obtained from field and commercial hatcheries; and strongly improve the applicability of the stable isotope method in understanding life-history and trophic ecology of fish populations. PMID:28046021

Lake Superior lipids

EPA Pesticide Factsheets

Fish chemistry data (d13C, d15N, C:N, lipid content) published in Rapid Commun. Mass Spectrom. 2015, 29, 2069??2077 DOI: 10.1002/rcm.7367This dataset is associated with the following publication:Hoffman , J., M. Sierszen , and A. Cotter. Fish tissue lipid-C:N relationships for correcting ä13C values and estimating lipid content in aquatic food web studies. Rapid Communications in Mass Spectrometry. Wiley InterScience, Silver Spring, MD, USA, 29(21): 2069–2077, (2015).

Study of the 20,22Ne+20,22Ne and 10,12,13,14,15C+12C Fusion Reactions with MUSIC

NASA Astrophysics Data System (ADS)

Avila, M. L.; Rehm, K. E.; Almaraz-Calderon, S.; Carnelli, P. F. F.; DiGiovine, B.; Esbensen, H.; Hoffman, C. R.; Jiang, C. L.; Kay, B. P.; Lai, J.; Nusair, O.; Pardo, R. C.; Santiago-Gonzalez, D.; Talwar, R.; Ugalde, C.

2016-05-01

A highly efficient MUlti-Sampling Ionization Chamber (MUSIC) detector has been developed for measurements of fusion reactions. A study of fusion cross sections in the 10,12,13,14,15C+12C and 20,22Ne+20,22Ne systems has been performed at ATLAS. Experimental results and comparison with theoretical predictions are presented. Furthermore, results of direct measurements of the 17O(α, n)20Ne, 23Ne(α, p)26Mg and 23Ne(α, n)26Al reactions will be discussed.

Flotsam samples can help explain the δ13C and δ15N values of invertebrate resting stages in lake sediment

NASA Astrophysics Data System (ADS)

van Hardenbroek, Maarten; Rinta, Päivi; Wooller, Matthew J.; Schilder, Jos; Stötter, Tabea; Heiri, Oliver

2018-06-01

The stable isotopic composition of chitinous remains of Cladocera (water fleas) and freshwater Bryozoa (moss animals) preserved in lake sediment records can provide supporting insights into past environmental and ecosystem changes in lakes. Here we explore whether analyses of these remains isolated from lake flotsam can provide information on the driving variables affecting the isotopic composition of these remains. We collected flotsam in 53 lakes and found enough material in 33 lakes to measure the stable carbon and nitrogen isotope ratios (expressed as δ13C and δ15N values, respectively) of resting stages. These values were compared with lake characteristics, water chemistry measurements, and the isotopic composition of sedimentary organic matter (SOM) in the lakes. Mean δ13C values of cladoceran ephippia and SOM were correlated and both were also negatively correlated with deep water methane concentrations and indicators of lake stratification. This supports the findings of previous studies that methane-derived carbon can provide a significant proportion of carbon entering planktonic food webs. Mean δ15N values of bryozoan statoblasts and SOM were correlated, suggesting that both reflect the δ15N values of phytoplankton. Our results provide information on how environmental variables in lakes can influence the δ13C and δ15N values in resting stages, but flotsam samples can also potentially be used to assess seasonal stable isotope variability of resting stages. Both types of information are important to improve palaeoenvironmental interpretations of stable isotope records based on these remains in lake sediments.

Synthesis and biosynthesis of {sup 13}C-, {sup 15}N-labeled deoxynucleosides useful for biomolecular structural determinations

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

Ashburn, D.A.; Garcia, K.; Hanners, J.L.

Currently, there is a great emphasis on elucidating the structure, function, and dynamics of DNA. Much of the research involved in this study uses nuclear magnetic resonance (NMR) spectroscopy. Effective use of NMR spectroscopy for DNA molecules with mw > 10,000 requires stable isotope enrichment. We present strategies for site-specific isotopic labeling of the purine bases adenosine and guanosine and the biosynthesis of (U-{sup 13}C, {sup 15}N) DNA from methylotropic bacteria. With commercially available 6-chloropurine, an effective two-step route leads to 2{prime}-deoxy-(amino-{sup 15}N)adenosine (dA). The resulting d(amino-{sup 15}N)A is used in a series of reactions to synthesize 2{prime}-deoxy-(2-{sup 13}C,1,amino-{sup 15}N{submore » 2})guanosine or any combination thereof. An improved biosynthesis of labeled DNA has been accomplished using Methylobacterium extorquens AS1. Each liter of growth medium contains 4 g of methanol to yield 1 g of lyophilized cells. As much as 200 mg of RNA per liter of culture has been obtained. We are currently developing large-scale isolation protocols. General synthetic pathways to oligomeric DNA will be presented.« less

The trophic ecology of key megafaunal species at the Pakistan Margin: Evidence from stable isotopes and lipid biomarkers

NASA Astrophysics Data System (ADS)

Jeffreys, Rachel M.; Wolff, George A.; Murty, Sarah J.

2009-10-01

The Arabian Sea is subject to intense seasonality resulting from biannual monsoons, which lead to associated large particulate fluxes and an abundance of organic carbon, a potential food source at the seafloor for benthic detritivores. We used the stable isotopes of carbon and nitrogen alongside lipid analyses to examine potential food sources (particulate and sedimentary organic matter, POM and SOM respectively) in order to determine trophic linkages for the twelve most abundant megafaunal species ( Pontocaris sp., Solenocera sp., Munidopsis aff. scobina, Actinoscyphia sp., Actinauge sp., Echinoptilum sp., Pennatula aff. grandis, Astropecten sp. Amphiura sp. Ophiura euryplax, Phormosoma placenta and Hyalinoecia sp.) at the Pakistan Margin between 140 and 1400 m water depth. This transect spans a steep gradient in oxygen concentrations and POM flux. Ranges of δ 13C and δ 15N values were narrow in POM and SOM (˜4‰ and ˜2‰ for δ 13C and δ 15N, respectively) with little evidence of temporal variability. Labile lipid compounds in SOM originating from phytoplankton did exhibit seasonal change in their concentrations at the shallowest sites, 140 and 300 m. Benthic megafauna had broad ranges in δ 13C and δ 15N (>10‰ and >8‰ for δ 13C and δ 15N, respectively) suggesting they occupy several trophic levels and utilize a variety of food sources. There is evidence for feeding niche separation between and within trophic groups. Lipid biomarkers in animal tissues indicate a mixture of food sources originating from both phytoplankton (C 20:5(n-3) and C 22:6(n-3)) and invertebrate prey (C 20:1 and C 22:1). Biomarkers originating from phytodetritus are conserved through trophic transfer to the predator/scavengers. Six species ( Pontocaris sp., Solenocera sp., Actinoscyphia sp., Echinoptilum sp., Amphiura sp. and Hyalinoecia sp.) showed a significant biochemical response to the seasonal supply of food and probably adapt their trophic strategy to low food availability. Biotransformation of assimilated lipids by megafauna is evident from polyunsaturated fatty acid distributions, for example, Echinoptilum sp. converts C 20:5(n-3) to C 24:6(n-3).

[Effects of nitrogen-supply levels on leaf senescence and characteristics of distribution and utilization of 13C and 15N in Fuji 3 apple grafted on different stocks].

PubMed

Chen, Qian; Ding, Ning; Zhu, Zhan Ling; Peng, Ling; Ge, Shun Feng; Jiang, Yuan Mao

2017-07-18

Two-year-old potted Fuji 3 apple trees on different rootstocks [Fuji 3/M. micromalus Makin (joe), Fuji 3/M7 (semi-dwarf) and Fuji 3/M26/M. micromalus Makin (dwarf)] were used to study leaf morphology and photosynthesis and the characteristics of distribution and utilization of 13 C and 15 N at different nitrogen supply levels (0N, 25%N and 100%N, the N content in 100% N treatment was the same as that in Hoagland complete nutrient solution) under sand culture condition. The main results were as follows: At shoot growth cessation stage in autumn, the leaf chlorophyll content (SPAD), leaf nitrogen content and photosynthetic rate were found the highest in Fuji 3/M. micromalus Makin, followed by Fuji 3/M7, and the lowest was found in Fuji 3/M26/M. micromalus Makin under the same nitrogen stress treatments (0N and 25%N), however, under normal nitrogen treatment (100%N) Fuji 3/M26/M. micromalus Makin had the highest leaf SPAD value, photosynthetic rate and the nitrogen content, followed by Fuji 3/M7, and the lowest was found in Fuji 3/M. micromalus Makin. The leaf SOD and CAT activities showed Fuji 3/M. micromalus Makin > Fuji 3/M7 > Fuji 3/M26/M. micromalus Makin under the same nitrogen stress treatments, but showed Fuji 3/M26/M. micromalus Makin > Fuji 3/M7 > Fuji 3/M. micromalus Makin under the normal nitrogen treatment. There were significant differences in the distributions of 15 N and 13 C in root and leaf in the 3 scion-stock combinations, and the distribution rates of 15 N and 13 C in roots were the highest under nitrogen stress treatments and in the order of Fuji 3/M. micromalus Makin > Fuji 3/M7 > Fuji 3/M26/M. micromalus Makin. The distribution rates of 15 N and 13 C in leaves were the highest under the normal nitrogen treatment and in the order of Fuji 3/M26/M. micromalus Makin > Fuji 3/M7 > Fuji 3/M. micromalus Makin. The 15 N utilization ratio differed significantly among the 3 scion-stock combinations under different nitrogen application levels and was in the order of Fuji 3/M. micromalus Makin (44.3%, 37.5% and 31.4%)> Fuji 3/M7 (38.8%,30.7% and 26.6%) > Fuji 3/M26/M. micromalus Makin (32.0%,27.2% and 22.5%).

Orientation and Order of the Amide Group of Sphingomyelin in Bilayers Determined by Solid-State NMR

PubMed Central

Matsumori, Nobuaki; Yamaguchi, Toshiyuki; Maeta, Yoshiko; Murata, Michio

2015-01-01

Sphingomyelin (SM) and cholesterol (Chol) are considered essential for the formation of lipid rafts; however, the types of molecular interactions involved in this process, such as intermolecular hydrogen bonding, are not well understood. Since, unlike other phospholipids, SM is characterized by the presence of an amide group, it is essential to determine the orientation of the amide and its order in the lipid bilayers to understand the nature of the hydrogen bonds in lipid rafts. For this study, 1′-13C-2-15N-labeled and 2′-13C-2-15N-labeled SMs were prepared, and the rotational-axis direction and order parameters of the SM amide in bilayers were determined based on 13C and 15N chemical-shift anisotropies and intramolecular 13C-15N dipole coupling constants. Results revealed that the amide orientation was minimally affected by Chol, whereas the order was enhanced significantly in its presence. Thus, Chol likely promotes the formation of an intermolecular hydrogen-bond network involving the SM amide without significantly changing its orientation, providing a higher order to the SM amide. To our knowledge, this study offers new insight into the significance of the SM amide orientation with regard to molecular recognition in lipid rafts, and therefore provides a deeper understanding of the mechanism of their formation. PMID:26083921

C, N, and O Isotopic Heterogeneities in Low-density Supernova Graphite Grains from Orgueil

NASA Astrophysics Data System (ADS)

Groopman, Evan; Bernatowicz, Thomas; Zinner, Ernst

2012-07-01

We report on the results of NanoSIMS isotope imaging of low-density supernova graphite grains from the Orgueil meteorite. 70 nm thick microtomed sections of three supernova graphite grains were deposited on Si wafers and isotopically imaged in the NanoSIMS. These sections contain hotspots of excesses in 18O and 15N, which are spatially well correlated, and are likely carried by internal TiC subgrains. These hotspots are considerably more enriched in 18O and 15N than the host graphite grain. Correlations between 18O and 15N excesses indicate that the grains incorporated material from the He/C supernova zone. Isotope images of the surfaces of some grains show heterogeneities in their N and O isotope compositions, with extreme excesses in 15N and 18O. In the microtome sections, we also observe two types of heterogeneities in the grains' C isotopic compositions: smooth, radial gradients in 12C/13C, with this ratio trending toward solar with increasing radius; and highly anomalous pockets up to 2 μm in size with 12C/13C Gt solar that are located near the centers of the grain sections. Partial isotopic equilibration does not likely explain the C isotopic heterogeneities. These grains and their constituent parts probably formed in a stellar environment with changing isotopic composition.

Multivariate carbon and nitrogen stable isotope model for the reconstruction of prehistoric human diet.

PubMed

Froehle, A W; Kellner, C M; Schoeninger, M J

2012-03-01

Using a sample of published archaeological data, we expand on an earlier bivariate carbon model for diet reconstruction by adding bone collagen nitrogen stable isotope values (δ(15) N), which provide information on trophic level and consumption of terrestrial vs. marine protein. The bivariate carbon model (δ(13) C(apatite) vs. δ(13) C(collagen) ) provides detailed information on the isotopic signatures of whole diet and dietary protein, but is limited in its ability to distinguish between C(4) and marine protein. Here, using cluster analysis and discriminant function analysis, we generate a multivariate diet reconstruction model that incorporates δ(13) C(apatite) , δ(13) C(collagen) , and δ(15) N holistically. Inclusion of the δ(15) N data proves useful in resolving protein-related limitations of the bivariate carbon model, and splits the sample into five distinct dietary clusters. Two significant discriminant functions account for 98.8% of the sample variance, providing a multivariate model for diet reconstruction. Both carbon variables dominate the first function, while δ(15) N most strongly influences the second. Independent support for the functions' ability to accurately classify individuals according to diet comes from a small sample of experimental rats, which cluster as expected from their diets. The new model also provides a statistical basis for distinguishing between food sources with similar isotopic signatures, as in a previously analyzed archaeological population from Saipan (see Ambrose et al.: AJPA 104(1997) 343-361). Our model suggests that the Saipan islanders' (13) C-enriched signal derives mainly from sugarcane, not seaweed. Further development and application of this model can similarly improve dietary reconstructions in archaeological, paleontological, and primatological contexts. Copyright © 2011 Wiley Periodicals, Inc.

A stable isotope study of fossil mammal remains from the Paglicci cave, Southern Italy. N and C as palaeoenvironmental indicators

NASA Astrophysics Data System (ADS)

Iacumin, P.; Bocherens, H.; Delgado Huertas, A.; Mariotti, A.; Longinelli, A.

1997-04-01

A set of 102 tooth and bone samples of Pleistocene age (32,600-13,300 yr BP) belonging to the species Cervus elaphus, Bos primigenius and Equus caballus and coming from the Paglicci cave (Southern Italy) was studied for the carbon (δ 13C) and nitrogen (δ 15N) isotopic composition of bone and dentine collage and for the carbon (δ 13C c) isotopic composition of tooth enamel carbonate. The amount of collagen extracted from bone and tooth samples (mg/g) was rather variable, representing approximately only 0.5-15% of the collagen present in a fresh bone. However, the loss of an important fraction of the original collagen during diagenesis did not change the in vivo isotopic composition. In general, when the δ 13C of both collagen and carbonate and the δ 15N of collagen obtained from each level for the three species are compared, wild ox shows the most increased values, deer the most decreased values and horse shows intermediate results. These differences are probably related to distinct diets or to differences in their physiological behaviour. However, the isotopic results suggest that the three species considered lived in an open environment with a diet based on C 3 plants. The stratigraphic sequence of light and heavy nitrogen isotope values between 19,000 and 15,000 may be related to shifts from arid to humid conditions, while the overall trend shown by δ 13C toward lighter values may be related to a progressive development of a forest habitat.

Nitrogen Isotopic Study of Benthic Macroalgae and Seawater in Biscayne Bay, Florida

NASA Astrophysics Data System (ADS)

Drayer, C. L.; Lamb, K. A.; Swart, P. K.; Altabet, M. A.; Anderson, W. T.; Bellmund, S.

2006-12-01

Biscayne Bay, Florida is a complex coastal environment with many possible natural and anthropogenic sources of nitrogen. Such sources include precipitation, N fixation, nutrient regeneration/recycling, landfill soil leaching, groundwater and agricultural runoff, septic tank leakage, and treated waste water effluent. In order to understand the relative importance of these various inputs, benthic macroalgae, seagrasses, and seawater samples were collected from Biscayne Bay transecting from canals through nearshore bay to offshore reef sites Macroalgae was identified by species, decarbonated, and analyzed for δ15N and δ13C. The mean δ15N and δ13C for the algal tissue were +5.4 (±0.3‰) and -15.1 (±0.1‰), respectively. Measured nearshore algal samples differed greatly from offshore samples and had a high δ15N value of +12.0 (±0.1‰) and a mean of +8.6 (±3.0‰), in comparison to offshore samples that averaged +4.7 (±2.5‰). Despite the variation in δ15N, the δ13C values for both nearshore and offshore samples fell within the accepted parameters for algal communities. Seawater was analyzed for δ15N in DIN (dissolved inorganic nitrogen) and DON (dissolved organic nitrogen) through the cadmium reduction method (Mcllvin and Altabet, 2005). The mean δ15N for the DIN was +4.5 (±3.9‰) and the DON was +5.8 (±3.3‰). Canal DON δ15N values contained the heaviest measured values at ~+18‰, while nearshore and offshore DON values were lighter, 4.9 (±1.6‰). DIN values were more spatially variable with canal and nearshore sites ranging from ~+10‰ through ~-4.5‰. This study will continue over the next two years to examine possible temporal C and N isotope variations and will expand to include a larger geographic region focusing on areas with high nutrient levels and harmful algae blooms (HABs).

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 nature of variation and the physiological processes responsible for stable isotope values from biological tissues are critical for their interpretation. Change in carbon and nitrogen stable isotopes (ΔδC13, Δδ15N) after lipid extraction for Tufted Puffins (Fratercula cirrhata) collected July 2010 at Attu Island, Aleutians.

Deuterium isotope effects on 13C and 15N chemical shifts of intramolecularly hydrogen-bonded enaminocarbonyl derivatives of Meldrum’s and Tetronic acid

NASA Astrophysics Data System (ADS)

Ullah, Saif; Zhang, Wei; Hansen, Poul Erik

2010-07-01

Secondary deuterium isotope effects on 13C and 15N nuclear shieldings in a series of cyclic enamino-diesters and enamino-esters and acyclic enaminones and enamino-esters have been examined and analysed using NMR and DFT (B3LYP/6-31G(d,p)) methods. One-dimensional and two-dimensional NMR spectra of enaminocarbonyl and their deuterated analogues were recorded in CDCl 3 and CD 2Cl 2 at variable temperatures and assigned. 1JNH coupling constants for the derivatives of Meldrum's and tetronic acids reveal that they exist at the NH-form. It was demonstrated that deuterium isotope effects, for the hydrogen bonded compounds, due to the deuterium substitution at the nitrogen nucleus lead to large one-bond isotope effects at nitrogen, 1Δ 15N(D), and two-bond isotope effects on carbon nuclei, 2ΔC(ND), respectively. A linear correlations exist between 2ΔC(ND) and 1Δ 15N(D) whereas the correlation with δNH is divided into two. A good agreement between the experimentally observed 2ΔC(ND) and calculated dσ 13C/dR NH was obtained. A very good correlation between calculated NH bond lengths and observed NH chemical shifts is found. The observed isotope effects are shown to depend strongly on Resonance Assisted Hydrogen bonding.

Structural determinants of Kvbeta1.3-induced channel inactivation: a hairpin modulated by PIP2.

PubMed

Decher, Niels; Gonzalez, Teresa; Streit, Anne Kathrin; Sachse, Frank B; Renigunta, Vijay; Soom, Malle; Heinemann, Stefan H; Daut, Jürgen; Sanguinetti, Michael C

2008-12-03

Inactivation of voltage-gated Kv1 channels can be altered by Kvbeta subunits, which block the ion-conducting pore to induce a rapid ('N-type') inactivation. Here, we investigate the mechanisms and structural basis of Kvbeta1.3 interaction with the pore domain of Kv1.5 channels. Inactivation induced by Kvbeta1.3 was antagonized by intracellular PIP(2). Mutations of R5 or T6 in Kvbeta1.3 enhanced Kv1.5 inactivation and markedly reduced the effects of PIP(2). R5C or T6C Kvbeta1.3 also exhibited diminished binding of PIP(2) compared with wild-type channels in an in vitro lipid-binding assay. Further, scanning mutagenesis of the N terminus of Kvbeta1.3 revealed that mutations of L2 and A3 eliminated N-type inactivation. Double-mutant cycle analysis indicates that R5 interacts with A501 and T480 of Kv1.5, residues located deep within the pore of the channel. These interactions indicate that Kvbeta1.3, in contrast to Kvbeta1.1, assumes a hairpin structure to inactivate Kv1 channels. Taken together, our findings indicate that inactivation of Kv1.5 is mediated by an equilibrium binding of the N terminus of Kvbeta1.3 between phosphoinositides (PIPs) and the inner pore region of the channel.

Inter-species and intra-annual variations of moss nitrogen utilization: Implications for nitrogen deposition assessment.

PubMed

Dong, Yu-Ping; Liu, Xue-Yan; Sun, Xin-Chao; Song, Wei; Zheng, Xu-Dong; Li, Rui; Liu, Cong-Qiang

2017-11-01

Moss nitrogen (N) concentrations and natural 15 N abundance (δ 15 N values) have been widely employed to evaluate annual levels and major sources of atmospheric N deposition. However, different moss species and one-off sampling were often used among extant studies, it remains unclear whether moss N parameters differ with species and different samplings, which prevented more accurate assessment of N deposition via moss survey. Here concentrations, isotopic ratios of bulk carbon (C) and bulk N in natural epilithic mosses (Bryum argenteum, Eurohypnum leptothallum, Haplocladium microphyllum and Hypnum plumaeforme) were measured monthly from August 2006 to August 2007 at Guiyang, SW China. The H. plumaeforme had significantly (P < 0.05) lower bulk N concentrations and higher δ 13 C values than other species. Moss N concentrations were significantly (P < 0.05) lower in warmer months than in cooler months, while moss δ 13 C values exhibited an opposite pattern. The variance component analyses showed that different species contributed more variations of moss N concentrations and δ 13 C values than different samplings. Differently, δ 15 N values did not differ significantly between moss species, and its variance mainly reflected variations of assimilated N sources, with ammonium as the dominant contributor. These results unambiguously reveal the influence of inter-species and intra-annual variations of moss N utilization on N deposition assessment. Copyright © 2017 Elsevier Ltd. All rights reserved.

Identification of energy consumption and nutritional stress by isotopic and elemental analysis of urine in bonobos (Pan paniscus).

PubMed

Deschner, Tobias; Fuller, Benjamin T; Oelze, Vicky M; Boesch, Christophe; Hublin, Jean-Jacques; Mundry, Roger; Richards, Michael P; Ortmann, Sylvia; Hohmann, Gottfried

2012-01-15

A mounting body of evidence suggests that changes in energetic conditions like prolonged starvation can be monitored using stable isotope ratios of tissues such as bone, muscle, hair, and blood. However, it is unclear if urinary stable isotope ratios reflect a variation in energetic condition, especially if these changes in energetic condition are accompanied by shifts in dietary composition. In a feeding experiment conducted on captive bonobos (Pan paniscus), we monitored urinary δ(13)C, δ(15)N, total C (carbon), total N (nitrogen), and C/N ratios and compared these results with glucocorticoid levels under gradually changing energy availability and dietary composition. Measurements of daily collected urine samples over a period of 31 days showed that while shifts in urinary isotope signatures of δ(13)C and δ(15)N as well as total C were best explained by changes in energy consumption, urinary total N excretion as well as the C/N ratios matched the variation in dietary composition. Furthermore, when correcting for fluctuations in dietary composition, the isotope signatures of δ(13)C and δ(15)N as well as total C correlated with urinary glucocorticoid levels; however, the urinary total N and the C/N ratio did not. These results indicate for the first time that it is possible to non-invasively explore specific longitudinal records on animal energetic conditions and dietary compositions with urinary stable isotope ratios and elemental compositions, and this research provides a strong foundation for investigating how ecological factors and social dynamics affect feeding habits in wild animal populations such as primates. Copyright © 2011 John Wiley & Sons, Ltd.

Insights into nutrient assimilation and export in naturally iron-fertilized waters of the Southern Ocean from nitrogen, carbon and oxygen isotopes

NASA Astrophysics Data System (ADS)

Trull, Thomas W.; Davies, Diana; Casciotti, Karen

2008-03-01

The KErguelen Ocean and Plateau compared Study (KEOPS) documented enhanced iron input and phytoplankton biomass over the deep Kerguelen plateau in comparison to surrounding high-nutrient low-chlorophyll (HNLC) waters in late summer 2005. We examined the influence of this iron on nitrogen and carbon metabolism by the microbial food-web, by comparing samples from on-plateau and off-plateau. Suspended particulate organic carbon (POC) was ˜5 times more abundant on-plateau and exhibited greater POC/PON (˜6.5 vs. ˜5.5), δ13C-POC (˜-21.5 vs. ˜-24.5‰) and δ15N-PON (˜+2 vs. ˜0‰) than off-plateau. These differences arose in part from changes in ecosystem structure as demonstrated by size-fractionation (1, 5, 20, 55, 210, and 335-μm filters in series), which revealed large isotopic variations with size ( δ13C-POC ranged from -28 to -19‰ and δ15N-PON from -3 to +5‰) and greater abundances of 13C- and 15N-enriched large phytoplankton over the plateau. The 13C enrichment in POC reflected faster growth rates and greater draw-down of dissolved inorganic carbon over the plateau. Quantitative comparison to the δ15N of dissolved nitrate indicates that the δ15N-PON enrichment derived from increased assimilation of nitrate, corresponding to new production f-ratios of 0.7-0.9 on-plateau vs. 0.4-0.6 off-plateau. Results from a sparse set of free-drifting sediment trap samples suggest control of export by zooplankton grazing. The 15N and 18O enrichments in dissolved nitrate exhibited a 1:1 correlation, indicating that phytoplankton assimilation controls nitrate availability and only a relatively small amount of nitrate was regenerated by nitrification. The δ15N-NO 3 values yield indistinguishable isotopic fractionation factors on and off the plateau ( 15ɛ of 4-5‰). This suggests that variations in iron availability may not bias the interpretation of paleo-environmental 15N records, and leaves intact the view that higher sedimentary δ15N-PON values during the last glacial maximum indicate greater fractional nitrate depletion in the Southern Ocean.

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

PubMed

Amelung, W; Bol, R; Friedrich, C

1999-01-01

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

Stable isotopes document the trophic structure of a deep-sea cephalopod assemblage including giant octopod and giant squid.

PubMed

Cherel, Y; Ridoux, V; Spitz, J; Richard, P

2009-06-23

Although deep-sea cephalopods are key marine organims, their feeding ecology remains essentially unknown. Here, we report for the first time the trophic structure of an assemblage of these animals (19 species) by measuring the isotopic signature of wings of their lower beaks, which accumulated in stomachs of stranded sperm whales. Overall, the species encompassed a narrow range in delta(13)C values (1.7 per thousand), indicating that they lived in closely related and overlapping habitats. delta(13)C values can be interpreted in terms of distribution with the more (13)C-depleted species (e.g. Stigmatoteuthis arcturi, Vampyroteuthis infernalis) having a more pelagic habitat than the more (13)C-enriched, bathyal species (e.g. Todarodes sagittatus and the giant squid Architeuthis dux). The cephalopods sampled had delta(15)N values ranging 4.6 per thousand, which is consistent with the species spanning approximately 1.5 trophic levels. Neither the giant octopod (Haliphron atlanticus) nor the giant squid reached the highest trophic position. Species delta(15)N was independent of body size, with large squids having both the highest (Taningia danae) and lowest (Lepidoteuthis grimaldii) delta(15)N values. Their trophic position indicates that some species share the top of the food web, together with other megacarnivores such as the sperm whale.

Environmental variables across Pan troglodytes study sites correspond with the carbon, but not the nitrogen, stable isotope ratios of chimpanzee hair.

PubMed

Schoeninger, Margaret J; Most, Corinna A; Moore, Jim J; Somerville, Andrew D

2016-10-01

Diet influences the stable isotope ratios of carbon and nitrogen (δ(13) C and δ(15) N values) in animal tissue; but here we explore the influences of particular aspects of the local environment on those values in chimpanzees (Pan troglodytes). In this article we present new δ(13) C and δ(15) N values in Gombe chimpanzees using hairs collected from night nests in 1989. Then, we explore the influence of environmental factors by comparing our Gombe data to those from eight additional Pan study sites with previously published stable isotope data. We compare chimpanzee δ(13) Chair and δ(15) Nhar values to specific characteristics of local site ecology (biome and ecoregion) and to local Mean Annual Precipitation (MAP) to test hypotheses based on known effects of these variables on the δ(13) C and δ(15) N values in plant tissues. The comparison shows that hair from chimpanzees living in savanna sites with lower MAP have higher δ(13) Chair values than do chimpanzees living in woodland and forested sites with higher MAP. These results demonstrate the potential of using δ(13) C values in primate tissue to indicate aspects of their local ecology in cases where the ecology is uncertain, such as samples collected early in the last century and in fossil hominins. In contrast to expectations, however, chimpanzee δ(15) Nhair values from some savanna sites with lower MAP are lower, not higher, than those living in more forested areas with higher MAP. It is likely that diet selectivity by chimpanzees affects δ(15) Nhair values to a greater extent than does the influence of precipitation on plants. Am. J. Primatol. 78:1055-1069, 2016. © 2015 Wiley Periodicals, Inc. © 2015 Wiley Periodicals, Inc.

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

NASA Astrophysics Data System (ADS)

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

2012-03-01

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

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

PubMed

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

2010-03-24

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

Accurate measurement of heteronuclear dipolar couplings by phase-alternating R-symmetry (PARS) sequences in magic angle spinning NMR spectroscopy

NASA Astrophysics Data System (ADS)

Hou, Guangjin; Lu, Xingyu; Vega, Alexander J.; Polenova, Tatyana

2014-09-01

We report a Phase-Alternating R-Symmetry (PARS) dipolar recoupling scheme for accurate measurement of heteronuclear 1H-X (X = 13C, 15N, 31P, etc.) dipolar couplings in MAS NMR experiments. It is an improvement of conventional C- and R-symmetry type DIPSHIFT experiments where, in addition to the dipolar interaction, the 1H CSA interaction persists and thereby introduces considerable errors in the dipolar measurements. In PARS, phase-shifted RN symmetry pulse blocks applied on the 1H spins combined with π pulses applied on the X spins at the end of each RN block efficiently suppress the effect from 1H chemical shift anisotropy, while keeping the 1H-X dipolar couplings intact. Another advantage over conventional DIPSHIFT experiments, which require the signal to be detected in the form of a reduced-intensity Hahn echo, is that the series of π pulses refocuses the X chemical shift and avoids the necessity of echo formation. PARS permits determination of accurate dipolar couplings in a single experiment; it is suitable for a wide range of MAS conditions including both slow and fast MAS frequencies; and it assures dipolar truncation from the remote protons. The performance of PARS is tested on two model systems, [15N]-N-acetyl-valine and [U-13C,15N]-N-formyl-Met-Leu-Phe tripeptide. The application of PARS for site-resolved measurement of accurate 1H-15N dipolar couplings in the context of 3D experiments is presented on U-13C,15N-enriched dynein light chain protein LC8.

Recent sedimentary history of organic matter and nutrient accumulation in the Ohuira Lagoon, northwestern Mexico.

PubMed

Ruiz-Fernández, Ana Carolina; Frignani, Mauro; Tesi, Tommaso; Bojórquez-Leyva, Humberto; Bellucci, Luca Giorgio; Páez-Osuna, Federico

2007-08-01

(210)Pb-derived sediment accumulation rates, as well as a suite of geochemical proxies (Al, Fe, delta(13)C, delta(15)N), were used to assess the time-dependent variations of C, N, and P fluxes recorded in two sediment cores collected at Ohuira Lagoon, in the Gulf of California, Mexico, during the last 100 years. Sedimentary C, N, and P concentrations increased with time and were related to land clearing, water impoundment, and agriculture practices, such as fertilization. C:N:P ratios and delta(13)C suggested an estuarine system that is responsive to increased C loading from a N-limited phytoplankton community, whereas delta(15)N values showed the transition between an estuarine-terrestrial to an estuarine-more marine environment, as a consequence of the declining freshwater supply into the estuary due to the channeling and impoundment of El Fuerte River between 1900 and 1956. The recent increases in nutrient fluxes (2- to 9-fold the pre-anthropogenic fluxes of C and N, and 2 to 13 times for P) taking place in the mainland from the 1940s, were related to the expansion of the intensive agriculture fields and to the more recent development of shrimp farming activities.

Carbon flux from plants to soil microbes is highly sensitive to nitrogen addition and biochar amendment

NASA Astrophysics Data System (ADS)

Kaiser, C.; Solaiman, Z. M.; Kilburn, M. R.; Clode, P. L.; Fuchslueger, L.; Koranda, M.; Murphy, D. V.

2012-04-01

The release of carbon through plant roots to the soil has been recognized as a governing factor for soil microbial community composition and decomposition processes, constituting an important control for ecosystem biogeochemical cycles. Moreover, there is increasing awareness that the flux of recently assimilated carbon from plants to the soil may regulate ecosystem response to environmental change, as the rate of the plant-soil carbon transfer will likely be affected by increased plant C assimilation caused by increasing atmospheric CO2 levels. What has received less attention so far is how sensitive the plant-soil C transfer would be to possible regulations coming from belowground, such as soil N addition or microbial community changes resulting from anthropogenic inputs such as biochar amendments. In this study we investigated the size, rate and sensitivity of the transfer of recently assimilated plant C through the root-soil-mycorrhiza-microbial continuum. Wheat plants associated with arbuscular mycorrhizal fungi were grown in split-boxes which were filled either with soil or a soil-biochar mixture. Each split-box consisted of two compartments separated by a membrane which was penetrable for mycorrhizal hyphae but not for roots. Wheat plants were only grown in one compartment while the other compartment served as an extended soil volume which was only accessible by mycorrhizal hyphae associated with the plant roots. After plants were grown for four weeks we used a double-labeling approach with 13C and 15N in order to investigate interactions between C and N flows in the plant-soil-microorganism system. Plants were subjected to an enriched 13CO2 atmosphere for 8 hours during which 15NH4 was added to a subset of split-boxes to either the root-containing or the root-free compartment. Both, 13C and 15N fluxes through the plant-soil continuum were monitored over 24 hours by stable isotope methods (13C phospho-lipid fatty acids by GC-IRMS, 15N/13C in bulk plant material, microbial biomass and dissolved organic matter by IRMS, 13C and 15N in plant roots cells and intraradical mycorrhizal hyphae by NanoSims). Our results show that (1) C assimilated by plants was delivered within 4 hours to the soil microbial community both via roots and the mycorrhizal network (2) N addition during the labeling period strongly and rapidly increased the 13C flux of recently assimilated carbohydrates to the soil microbial biomass (3) the effect of N addition was not as rapid but was of the same magnitude when N was delivered to the plant exclusively by mycorrhizal hyphae as compared to taken up by roots (4) soils which had been amended with biochar (which were characterized by an increased abundance of mycorrhizal fungi) also showed a significant increase of C flux from plants to the soil. We conclude that plant belowground C allocation is highly sensitive to alterations of microbial community structure and nutritional status in the soil. Moreover, our results indicate that plants respond rapidly (within hours) to changing soil N availability by altering the rate of C transported belowground. Our results emphasise the ecological significance of plant-belowground interactions for ecosystem C cycling.

Hydrological and Biogeochemical Controls on Seasonal and Spatial Differences in Food Webs in the Everglades

NASA Astrophysics Data System (ADS)

Kendall, C.; Wankel, S. D.; Bemis, B. E.; Rawlik, P. S.; Krabbenhoft, D. P.; Lange, T.

2002-05-01

Stable isotopes can be used to determine the relative trophic positions of biota within a food web, and to improve our understanding of the biomagnification of contaminants. Plants at the base of the food web uptake dissolved organic carbon (DIC) and nitrogen (DIN) for growth, and their tissue reflects the isotopic composition of these sources. Animals then mirror the isotopic composition of the primary producers, as modified by consumer-diet fractionations at successive trophic steps. During 1995-99, we collected algae, macrophyte, invertebrate, and fish samples from 15 USGS sites in the Everglades and analyzed them for d13C and d15N with the goal of characterizing seasonal and spatial differences in food web relations. Carbon isotopes effectively distinguish between two main types of food webs: ones where algae is the dominant base of the food web, which are characteristic of relatively pristine marsh sites with long hydroperiods, and ones where macrophyte debris appears to be a significant source of nutrients, which are apparently characteristic of shorter hydroperiod sites, and nutrient-impacted marshes and canals. There usually is an inverse relation between d13C and d15N of organisms over time, especially in more pristine environments, reflecting seasonal changes in the d13C of DIC and the d15N of DIN. The d13C and d15N of algae also show strong positive correlations with seasonal changes in water levels. This variability is substantially damped up the food chain, probably because of the longer integration times of animals vs. plants. We speculate that these seasonal shifts in water level result in changes in biogeochemical reactions and nutrient levels, with corresponding variations in the d15N and d13C of biota. For example, small changes in water level may change the balance of photosynthesis, bacterial respiration, and atmospheric exchange reactions that control the d13C of DIC. Such changes will probably also affect the d15N of dissolved inorganic N (DIN) because of corresponding changes in N uptake and redox conditions. During the dry season, the marshes probably become more anoxic because of shallower water levels, less photosynthesis, and increased quantities of decaying vegetation. During this season, macrophyte debris appears to be a significant source of nutrients to local food webs. Our isotope data are consistent with seasonal differences in food webs, related to seasonal differences in water levels. Hence, biota isotopes provide a powerful tool for monitoring how future ecosystem changes, in particular changes in hydroperiod, will affect food webs across the Everglades.

Last millennium environmental changes and climate inferences in the Southeastern Atlantic forest, Brazil.

PubMed

Pessenda, Luiz C R; Saia, Soraya E M G; Gouveia, Susy E M; Ledru, Marie-Pierre; Sifeddine, Abdelfettah; Amaral, Paula G C; Bendassolli, José A

2010-09-01

This study presents paleoenvironmental data based on pollen, elemental and isotopic compositions of organic matter (TOC, N, δ(13)C and δ(15)N) and (14)C dating of 170 cm lake sediment record. Samplings have been made in Lagoa Grande at Parque Estadual Turístico do Alto Ribeira - PETAR, Southern São Paulo State, Southeastern Brazil. The variations in relative frequencies (in percentage) of arboreal pollen along the core range between 40 and 80%. The δ(13)C values ranged from -23% to -30% and C/N of ~10 to 15, indicating the contribution of terrestrial C(3) plants and algae in the sediment organic matter. The δ(15)N results presented values from 3 to 4.5%, also suggesting a mixture of algae and terrestrial C(3) plants. The (14)C dating indicates modern age for the shallow horizons to ~1030 BP at the base of the core. A probable wetter climate in the period of ~370 BP to ~340 BP was inferred from the data set, which corresponds to a part of the period covered by the Little Ice Age (LIA).

Dual Roles of β-Oxodithioesters in the Copper-Catalyzed Synthesis of Benzo[e]pyrazolo[1,5-c][1,3]thiazine Derivatives.

PubMed

Wen, Li-Rong; Yuan, Wen-Kui; Li, Ming

2015-05-15

A facile and efficient method for the chemoselective synthesis of benzo[e]pyrazolo[1,5-c][1,3]thiazine derivatives has been developed by tandem Ullmann coupling reactions of β-oxodithioesters (ODEs) with 3-(2-bromoaryl)-1H-pyrazoles in C-S bond formation manner, in which ODEs play dual roles as both a substrate and a ligand. A series of benzo[e]pyrazolo[1,5-c][1,3]thiazine derivatives were provided in good to excellent yields with CuI as the copper source in the presence of NaOH in CH3CN at 80 °C under a N2 atmosphere.

The nature of organic carbon in density-fractionated sediments in the Sacramento-San Joaquin River Delta (California)

NASA Astrophysics Data System (ADS)

Wakeham, S. G.; Canuel, E. A.

2016-02-01

Rivers are the primary means by which sediments and carbon are transported from the terrestrial biosphere to the oceans but gaps remain in our understanding of carbon associations from source to sink. Bed sediments from the Sacramento-San Joaquin River Delta (CA) were fractionated according to density and analyzed for sediment mass distribution, elemental (C and N) composition, mineral surface area, and stable carbon and radiocarbon isotope compositions of organic carbon (OC) and fatty acids to evaluate the nature of organic carbon in river sediments. OC was unevenly distributed among density fractions. Mass and OC were in general concentrated in mesodensity (1.6-2.0 and 2.0-2.5 g cm-3) fractions, comprising 84.0 ± 1.3 % of total sediment mass and 80.8 ± 13.3 % of total OC (TOC). Low-density (< 1.6 g cm-3) material, although rich in OC (34.0 ± 2.0 % OC) due to woody debris, constituted only 17.3 ± 12.8 % of TOC. High-density (> 2.5 g cm-3) organic-poor, mineral-rich material made-up 13.7 ± 1.4 % of sediment mass and 2.0 ± 0.9 % of TOC. Stable carbon isotope compositions of sedimentary OC were relatively uniform across bulk and density fractions (δ13C -27.4 ± 0.5 ‰). Radiocarbon content varied from Δ14C values of -382 (radiocarbon age 3800 yr BP) to +94 ‰ (modern) indicating a mix of young and old OC. Fatty acids were used to further constrain the origins of sedimentary OC. Short-chain n-C14-n-C18 fatty acids of algal origin were depleted in 13C (δ13C -37.5 to -35.2 ‰) but were enriched in 14C (Δ14C > 0) compared to long-chain n-C24-n-C28 acids of vascular plant origins with higher δ13C (-33.0 to -31.0 ‰) but variable Δ14C values (-180 and 61 ‰). These data demonstrate the potentially complex source and age distributions found within river sediments and provide insights about sediment and organic matter supply to the Delta.

Backbone amide 15N chemical shift tensors report on hydrogen bonding interactions in proteins: A magic angle spinning NMR study.

PubMed

Paramasivam, Sivakumar; Gronenborn, Angela M; Polenova, Tatyana

2018-08-01

Chemical shift tensors (CSTs) are an exquisite probe of local geometric and electronic structure. 15 N CST are very sensitive to hydrogen bonding, yet they have been reported for very few proteins to date. Here we present experimental results and statistical analysis of backbone amide 15 N CSTs for 100 residues of four proteins, two E. coli thioredoxin reassemblies (1-73-(U- 13 C, 15 N)/74-108-(U- 15 N) and 1-73-(U- 15 N)/74-108-(U- 13 C, 15 N)), dynein light chain 8 LC8, and CAP-Gly domain of the mammalian dynactin. The 15 N CSTs were measured by a symmetry-based CSA recoupling method, ROCSA. Our results show that the principal component δ 11 is very sensitive to the presence of hydrogen bonding interactions due to its unique orientation in the molecular frame. The downfield chemical shift change of backbone amide nitrogen nuclei with increasing hydrogen bond strength is manifested in the negative correlation of the principal components with hydrogen bond distance for both α-helical and β-sheet secondary structure elements. Our findings highlight the potential for the use of 15 N CSTs in protein structure refinement. Copyright © 2018 Elsevier Inc. All rights reserved.

Mercury concentrations in Southern Beaufort Sea polar bears: variation based on stable isotopes of carbon and nitrogen.

PubMed

Cardona-Marek, Tamara; Knott, Katrina K; Meyer, Benjamin E; O'Hara, Todd M

2009-07-01

Total Hg concentration was measured in hair and whole blood of 52 adult Southern Beaufort Sea polar bears (Ursus maritimus) captured in the spring of 2005. Stable isotopic signatures (i.e., 13C/12C, delta13C; 15N/14N, delta15N) in hair and two blood compartments (packed blood cells/clot and serum) were determined to assess the variation of Hg concentrations among polar bears in relation to their feeding ecology and other biological factors. Concentrations of Hg in hair and blood (2.2-23.9 microg/g dry wt and 0.007-0.213 microg/g wet wt, respectively) were within the range of values previously reported for polar bears in Canada and East Greenland. Mercury concentration in hair from females was higher than that in hair from males, and concentration was related to interactions between delta13C, delta15N, and longitude of capture location. Mercury concentrations in hair were inversely correlated to delta13C in hair and blood, suggesting that polar bears with greater total Hg concentrations fed more on pelagic prey, such as ringed seals or beluga whale, than on benthic prey. Variability in Hg concentrations in polar bear hair and blood may be the result of intraspecific or regional variation in prey selection rather than strictly trophic level interactions.

Disentangling a rainforest food web using stable isotopes: dietary diversity in a species-rich ant community.

PubMed

Blüthgen, Nico; Gebauer, Gerhard; Fiedler, Konrad

2003-11-01

For diverse communities of omnivorous insects such as ants, the extent of direct consumption of plant-derived resources vs. predation is largely unknown. However, determination of the extent of "herbivory" among ants may be crucial to understand the hyper-dominance of ants in tropical tree crowns, where prey organisms tend to occur scarcely and unpredictably. We therefore examined N and C stable isotope ratios (delta(15)N and delta(13)C) in 50 ant species and associated insects and plants from a tropical rainforest in North Queensland, Australia. Variation between ant species was pronounced (range of species means: 7.1 per thousand in delta(15)N and 6.8 per thousand in delta(13)C). Isotope signatures of the entire ant community overlapped with those of several herbivorous as well as predacious arthropods. Variability in delta(15)N between ants was not correlated with plant delta(15)N from which they were collected. Ant species spread out in a continuum between largely herbivorous and purely predacious taxa, with a high degree of omnivory. Ant species' delta(15)N were consistent with the trophic level predicted by natural feeding observations, but not their delta(13)C. Low delta(15)N levels were recorded for ant species that commonly forage for nectar on understorey or canopy plants, intermediate levels for species with large colonies that were highly abundant on nectar and honeydew sources and were predacious, and the highest levels for predominantly predatory ground-foraging species. Colonies of the dominant weaver-ants (Oecophylla smaragdina) had significantly lower delta(15)N in mature forests (where preferred honeydew and nectar sources are abundant) than in open secondary vegetation. N concentration of ant dry mass showed only very limited variability across species and no correlation with trophic levels. This study demonstrates that stable isotopes provide a powerful tool for quantitative analyses of trophic niche partitioning and plasticity in complex and diverse tropical omnivore communities.

First Measurement of the 14N/15N Ratio in the Analog of the Sun Progenitor OMC-2 FIR4

NASA Astrophysics Data System (ADS)

Kahane, Claudine; Jaber Al-Edhari, Ali; Ceccarelli, Cecilia; López-Sepulcre, Ana; Fontani, Francesco; Kama, Mihkel

2018-01-01

We present a complete census of the 14N/15N isotopic ratio in the most abundant N-bearing molecules toward the cold envelope of the protocluster OMC-2 FIR4, the best known Sun progenitor. To this scope, we analyzed the unbiased spectral survey obtained with the IRAM 30 m telescope at 3, 2, and 1 mm. We detected several lines of CN, HCN, HNC, HC3N, N2H+, and their respective 13C and 15N isotopologues. The lines’ relative fluxes are compatible with LTE conditions, and moderate line opacities have been corrected via a population diagram method or theoretical relative intensity ratios of the hyperfine structures. The five species lead to very similar 14N/15N isotopic ratios, without any systematic difference between amine- and nitrile-bearing species as previously found in other protostellar sources. The weighted average of the 14N/15N isotopic ratio is 270 ± 30. This 14N/15N value is remarkably consistent with the [250–350] range measured for the local galactic ratio but significantly differs from the ratio measured in comets (around 140). High-angular resolution observations are needed to examine whether this discrepancy is maintained at smaller scales. In addition, using the CN, HCN, and HC3N lines, we derived a 12C/13C isotopic ratio of 50 ± 5.

Backbone chemical shift assignments for the sensor domain of the Burkholderia pseudomallei histidine kinase RisS: "missing" resonances at the dimer interface.

PubMed

Buchko, Garry W; Edwards, Thomas E; Hewitt, Stephen N; Phan, Isabelle Q H; Van Voorhis, Wesley C; Miller, Samuel I; Myler, Peter J

2015-10-01

Using a deuterated sample, all the observable backbone (1)H(N), (15)N, (13)C(a), and (13)C' chemical shifts for the dimeric, periplasmic sensor domain of the Burkholderia pseudomallei histidine kinase RisS were assigned. Approximately one-fifth of the amide resonances are "missing" in the (1)H-(15)N HSQC spectrum and map primarily onto α-helices at the dimer interface observed in a crystal structure suggesting this region either undergoes intermediate timescale motion (μs-ms) and/or is heterogeneous.

Investigating economic specialization on the central Peruvian coast: A reconstruction of Late Intermediate Period Ychsma diet using stable isotopes.

PubMed

Marsteller, Sara J; Zolotova, Natalya; Knudson, Kelly J

2017-02-01

Hypothetical models of socioeconomic organization in pre-Columbian societies generated from the rich ethnohistoric record in the New World require testing against the archaeological and bioarchaeological record. Here, we test ethnohistorian Maria Rostworowski's horizontality model of socioeconomic specialization for the Central Andean coast by reconstructing dietary practices in the Late Intermediate Period (c. AD 900-1470) Ychsma polity to evaluate complexities in social behaviors prior to Inka imperial influence. Stable carbon and nitrogen isotope analysis of archaeological human bone collagen and apatite (δ 13 C col[VPDB], δ 15 N col[AIR] , δ 13 C ap[VPDB] ) and locally available foods is used to reconstruct the diets of individuals from Armatambo (n = 67), associated ethnohistorically with fishing, and Rinconada Alta (n = 46), associated ethnohistorically with agriculture. Overall, mean δ 15 N col[AIR] is significantly greater at Armatambo, while mean δ 13 C col[VPDB] and mean δ 13 C ap[VPDB] are not significantly different between the two sites. Within large-scale trends, adult mean δ 13 C ap[VPDB] is significantly greater at Armatambo. In addition, nearly one-third of Armatambo adults and adolescents show divergent δ 15 N col[AIR] values. These results indicate greater reliance on marine resources at Armatambo versus Rinconada Alta, supporting the ethnohistoric model of socioeconomic specialization for the Central Andean coast. Deviations from large-scale dietary trends suggest complexities not accounted for by the ethnohistoric model, including intra-community subsistence specialization and/or variation in resource access. © 2016 Wiley Periodicals, Inc.

Fresno Air Terminal, California. Revised Uniform Summary of Surface Weather Observations (RUSSWO). Parts A-F

DTIC Science & Technology

1981-01-15

34 *,"- *< " + "-o:"- I *13 C. -"-d+J °0 ’ A4 *+ *" - "~ ._______+: .+ ..G+ ., .2+ .- + tD .: rrgC 67 .. .+ .- -- T C’ TRAC 690 l1ei1. -+ _ *d ef . 5 .t CU L...3;M’d4 JitrET&: SURFACE WINDS 11 Z TD ,T-.[ 5IVIIE/A: PERCENTAGE FREQUENCY OF WIND DIRECTION AND SPEED (FROM HOURLY OBSEVATIONS) STATIO1N V"AT O NAM...041.5 (OL.A) PNvICUs contom1co tins JooN om ossouiti A I - - - - - -- - - - - - - - - - - -__ _ _ _ _ _ _ _ _ _ -_ _ _ _ U : LI4& TD ...3SY 3RA4𔃾 -211

Lithium-Rich Nanoscale Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 Cathode Material Prepared by Co-Precipitation Combined Freeze Drying (CP-FD) for Lithium-Ion Batteries

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

Bai, Ying; Li, Yu; Wu, Chuan

Nanoscale Li-rich Li1.2Mn0.54Ni0.13Co0.13O2 material is synthesized by a co-precipitation combined freeze drying (CP-FD) method, and compared with a conventional co-precipitation method combined vacuum drying (CP-VD). With the combination of X-ray diffraction (XRD) and scanning electron microscopy (SEM), it is found that the sample from CP-FD method consists of a pure phase with good crystallinity and small, homogenous particles (100-300 nm) with uniform particle size distribution. Inductively coupled plasma spectroscopy (ICP) shows that the sample has a stoichiometric ratio of n((Li)): n((Mn)): n((Ni)): n((Co))=9: 4: 1: 1; and its Brunauer-Emmett-Teller (BET) specific surface area is 5.749 m(2)g(-1). This sample achieves excellentmore » electrochemical properties: its initial discharge capacities are 298.9 mAhg(-1) at 0.1C (20 mAg(-1)), 246.1 mAhg(-1) at 0.5C, 215.8 mAhg(-1) at 1C, and 154.2 mAhg(-1) at 5C (5C charge and 5C discharge), as well as good cycling performance. In addition, the Li+ chemical diffusion coefficient of Li1.2Mn0.54Ni0.13Co0.13O2 material prepared by the CP-FD method is 4.59 x 10(-11) cm(2) s(-1), which is higher than that of the Li1.2Mn0.54Ni0.13Co0.13O2 material prepared by CP-VD. This phenomenon illustrates the potential for Li1.2Mn0.54Ni0.13Co0.13O2 with good rate performance synthesized by CP-FD method.« less

Long-term nitrogen deposition linked to reduced water use efficiency in forests with low phosphorus availability.

PubMed

Huang, Zhiqun; Liu, Bao; Davis, Murray; Sardans, Jordi; Peñuelas, Josep; Billings, Sharon

2016-04-01

The impact of long-term nitrogen (N) deposition is under-studied in phosphorus (P)-limited subtropical forests. We exploited historically collected herbarium specimens to investigate potential physiological responses of trees in three subtropical forests representing an urban-to-rural gradient, across which N deposition has probably varied over the past six decades. We measured foliar [N] and [P] and stable carbon (δ(13) C), oxygen (δ(18) O) and nitrogen (δ(15) N) isotopic compositions in tissue from herbarium specimens of plant species collected from 1947 to 2014. Foliar [N] and N : P increased, and δ(15) N and [P] decreased in the two forests close to urban centers. Consistent with recent studies demonstrating that N deposition in the region is (15) N-depleted, these data suggest that the increased foliar [N] and N : P, and decreased [P], may be attributable to atmospheric deposition and associated enhancement of P limitation. Estimates of intrinsic water use efficiency calculated from foliar δ(13) C decreased by c. 30% from the 1950s to 2014, contrasting with multiple studies investigating similar parameters in N-limited forests. This effect may reflect decreased photosynthesis, as suggested by a conceptual model of foliar δ(13) C and δ(18) O. Long-term N deposition may exacerbate P limitation and mitigate projected increases in carbon stocks driven by elevated CO2 in forests on P-limited soils. © 2015 The Authors. New Phytologist © 2015 New Phytologist Trust.

Variation in the mobilization of mercury into Black-winged Stilt Himantopus himantopus chicks in coastal saltpans, as revealed by stable isotopes

NASA Astrophysics Data System (ADS)

Tavares, P. C.; Kelly, A.; Maia, R.; Lopes, R. J.; Serrão Santos, R.; Pereira, M. E.; Duarte, A. C.; Furness, R. W.

2008-03-01

Causes of variation in mobilization of mercury into Black-winged Stilt Himantopus himantopus chicks were studied through analysis of stable isotope ratios of carbon and nitrogen. Blood and breast feathers were collected from chicks in coastal saltpans during successive breeding seasons. Detritus samples and potential prey (macroinvertebrates) were also collected. Total mercury concentrations and stable isotope signatures were measured using atomic absorption spectroscopy and isotope ratio mass spectrometry respectively. Mercury levels in Chironomidae, Corixidae and Hydrophilidae correlated with mercury levels in chick feathers. Differences of δ 15N signatures between macroinvertebrate groups indicated that they belong to different trophic levels. δ 15N signatures of invertebrates correlated with mercury levels in invertebrates and chicks, but not with δ 15N signatures in chicks. Between-group and between-site differences of δ 15N signatures and mercury levels in invertebrates suggested that they contribute differently to mercury mobilization into chicks, and their relative contribution depends on prey availability in each site. Inter-site differences in the biomagnification factor reinforced that idea. δ 13C signatures in invertebrates marked a larger range of carbon sources than just detritus. Variation of water inflow regime and prey availability may cause between-group and between-site differences of δ 13C signatures in prey. Discrepancies between feather and blood for δ 13C signatures in Praias-Sado and Vaia suggested that temporal variation of prey availability may be the main factor affecting mercury mobilization into chicks in both those cases, since their water inflow regimes are the same. The lowest levels of δ 13C signatures in Vau suggested that water inflow regime may be the main factor in this case, since no discrepancy existed in δ 13C signatures between blood and feather.

Analyses of barley spike mutant waxes identify alkenes, cyclopropanes and internally branched alkanes with dominating isomers at carbon 9.

PubMed

von Wettstein-Knowles, Penny

2007-01-01

About 15% of the epidermal wax on Hordeum vulgare cv. Bonus barley spikes is n-alkanes. Longer homologues are greatly reduced in the eceriferum mutants, cer-a(6), cer-e(8), cer-n(26), cer-n(53), cer-n(985), cer-x(60), cer-yc(135) and cer-yl(187). Simultaneously hydrocarbons accounting for only traces in the wild-type become prominent in the mutants, although their chain-length distributions remain unchanged. Accordingly several new hydrocarbon series were identified. The two major ones were C(23)-C(35)cis monoenoic alkenes (the major 9-ene isomer was part of a homologous series including 11, 13 and 15-enes), and the novel C(27)-C(31) cyclopropanes (the ring carbons of major isomers were 9,10 and 11,12 with lesser amounts of 13,14). Three minor series included 2- and 3-methylalkanes plus C(25)-C(33) internally branched alkanes (methyls on carbons 9, 11, 13, 15 or 17; shorter homologues dominated by the 9 isomer, longer homologues by 11, 13 or 15 isomers). Acyl chains destined for spike waxes are synthesized via acyl and polyketide elongase systems plus associated reductive and decarbonylative/decarboxylative enzyme systems. Both elongation systems are defective in synthesizing C(32) acyl chains in all nine mutants. The similarities in the position of the chemical groups (primarily on carbon 9, secondarily on carbon 11) of the alkenes, cyclopropanes and internally branched methyl alkanes imply an origin from a common, hitherto unrecognized associated pathway in barley, designated the enoic pathway. The elongation system leading to the enoic derived hydrocarbons differs from the known elongation systems by inclusion of a mechanism for introducing a double bond.

Isotopic characterization of flight feathers in two pelagic seabirds: Sampling strategies for ecological studies

USGS Publications Warehouse

Wiley, Anne E.; Ostrom, Peggy H.; Stricker, Craig A.; James, Helen F.; Gandhi, Hasand

2010-01-01

We wish to use stable-isotope analysis of flight feathers to understand the feeding behavior of pelagic seabirds, such as the Hawaiian Petrel (Pterodroma sandwichensis) and Newell’s Shearwater (Puffinus auricularis newelli). Analysis of remiges is particularly informative because the sequence and timing of remex molt are often known. The initial step, reported here, is to obtain accurate isotope values from whole remiges by means of a minimally invasive protocol appropriate for live birds or museum specimens. The high variability observed in D13C and D15N values within a feather precludes the use of a small section of vane. We found the average range within 42 Hawaiian Petrel remiges to be 1.3‰ for both D13C and D15N and that within 10 Newell’s Shearwater remiges to be 1.3‰ and 0.7‰ for D13C and D15N, respectively. The D13C of all 52 feathers increased from tip to base, and the majority of Hawaiian Petrel feathers showed an analogous trend in D15N. Although the average range of DD in 21 Hawaiian Petrel remiges was 11‰, we found no longitudinal trend. We discuss influences of trophic level, foraging location, metabolism, and pigmentation on isotope values and compare three methods of obtaining isotope averages of whole feathers. Our novel barb-sampling protocol requires only 1.0 mg of feather and minimal preparation time. Because it leaves the feather nearly intact, this protocol will likely facilitate obtaining isotope values from remiges of live birds and museum specimens. As a consequence, it will help expand the understanding of historical trends in foraging behavior

Blytheville AFB, Arkansas, Revised Uniform Summary of Surface Weather Observations (RUSSWO). Parts A-F.

DTIC Science & Technology

1987-10-01

A USAFETAC Air Weather Service (MAC) 3SSTAe’ REVISED UNIFORM SUMMARY OF SURFACE WEATHER OBSERVATIONS BLYTHEVILLE AFB AR MSC 1723408 IC N 35 58 W...I IE C It I 1-3 4-b I-Il It 1 7-2 1 2 - 4- UC 4 1-4 7 4F - U S5 1(IA " SAN I9 I 1. . 217 2.0 .i D I .lF I .2 1.? .7 1 .1 1 .2 .2- 0.1I 7 I AIR4 3tf...o o o , . . .. . . .o ..oo.o.. 17-, -7 5C.-. 1-7 ’-, F t tt 71*1. Li I I L C1.2 4 t 7 1L 1 4 uC I* I. A .o o.....oo. oo ~ oo o ooo ...... ...... .o. o

Orphan spin operators enable the acquisition of multiple 2D and 3D magic angle spinning solid-state NMR spectra

NASA Astrophysics Data System (ADS)

Gopinath, T.; Veglia, Gianluigi

2013-05-01

We propose a general method that enables the acquisition of multiple 2D and 3D solid-state NMR spectra for U-13C, 15N-labeled proteins. This method, called MEIOSIS (Multiple ExperIments via Orphan SpIn operatorS), makes it possible to detect four coherence transfer pathways simultaneously, utilizing orphan (i.e., neglected) spin operators of nuclear spin polarization generated during 15N-13C cross polarization (CP). In the MEIOSIS experiments, two phase-encoded free-induction decays are decoded into independent nuclear polarization pathways using Hadamard transformations. As a proof of principle, we show the acquisition of multiple 2D and 3D spectra of U-13C, 15N-labeled microcrystalline ubiquitin. Hadamard decoding of CP coherences into multiple independent spin operators is a new concept in solid-state NMR and is extendable to many other multidimensional experiments. The MEIOSIS method will increase the throughput of solid-state NMR techniques for microcrystalline proteins, membrane proteins, and protein fibrils.

Field evidence of differential food utilization of phytal harpacticoids collected from Fucus serratus indicated by δ 13C and δ 15N stable isotopes

NASA Astrophysics Data System (ADS)

Steinarsdóttir, M. B.; Ingólfsson, A.; Ólafsson, E.

2010-06-01

The present study is the first to compare trophic relationships of several co-occurring phytal harpacticoid species, in their natural habitat, using both δ 13C and δ 15N signatures. Three phytal harpacticoid species/taxa ( Zaus spinatus, Tisbe spp., and Parathalestris cf. intermedia) all collected from the alga Fucus serratus, at different times of the year, were analyzed. The results indicated that the harpacticoids were utilizing food sources differently. Specific food sources of the three species/taxa could not be accurately pinpointed, but there were strong indications that F. serratus and fragments from it did contribute significantly to the diet of P. cf. intermedia and Tisbe spp. Both of these harpacticoid species overlapped in δ 13C and δ 15N values with some of the macrofaunal species, collected from the same site in Hvassahraun, Iceland, while no overlap was seen for Z. spinatus. The signatures for Z. spinatus indicated that its food sources changed seasonally.

Recording 13C-15N HMQC 2D sparse spectra in solids in 30 s

NASA Astrophysics Data System (ADS)

Kupče, Ēriks; Trébosc, Julien; Perrone, Barbara; Lafon, Olivier; Amoureux, Jean-Paul

2018-03-01

We propose a dipolar HMQC Hadamard-encoded (D-HMQC-Hn) experiment for fast 2D correlations of abundant nuclei in solids. The main limitation of the Hadamard methods resides in the length of the encoding pulses, which results from a compromise between the selectivity and the sensitivity due to losses. For this reason, these methods should mainly be used with sparse spectra, and they profit from the increased separation of the resonances at high magnetic fields. In the case of the D-HMQC-Hn experiments, we give a simple rule that allows directly setting the optimum length of the selective pulses, versus the minimum separation of the resonances in the indirect dimension. The demonstration has been performed on a fully 13C,15N labelled f-MLF sample, and it allowed recording the build-up curves of the 13C-15N cross-peaks within 10 min. However, the method could also be used in the case of less sensitive samples, but with more accumulations.

Enantiomeric resolution of methylamphetamine and ephedrine: does this affect the δ13 C, δ15 N and δ2 H stable isotope ratios of the product?

PubMed

Grzechnik, Alexandra K; George, Adrian V; Mitchell, Linda; Collins, Michael; Salouros, Helen

2018-05-22

The use of stable isotope ratio mass spectrometry as a profiling tool for methylamphetamine has evolved over the last decade. Stable isotope ratios of carbon (δ 13 C), nitrogen (δ 15 N) and hydrogen (δ 2 H) of methylamphetamine are useful in determining the precursor used to manufacture methylamphetamine, and in many cases the synthetic origin of the methylamphetamine precursor. More recently samples of seized methylamphetamine show that a resolution step is being employed in the manufacturing process. We sought to determine whether the δ 13 C, δ 15 N and δ 2 H values were affected by either a resolution performed on racemic methylamphetamine or a resolution on racemic ephedrine, a commonly used precursor to methylamphetamine. We found that for the types of resolution studied, IRMS is still able to provide useful information on the provenance of a methylamphetamine sample. This article is protected by copyright. All rights reserved.

Hunter AAF, Savannah, Georgia. Revised Uniform Summary of Surface Weather Observations (RUSSWO)

DTIC Science & Technology

1970-11-18

Center of AIT/I.1Q-11 No Chile 13 Ft. to F~po 62 Rnwy 6 mar 62 Located 471 pt. 883 of Ros. No Chgc No Chile 15 Ft. to Feb 67 7 Mar 67 1. Located 300 Ft...N of lbwy 09 No Chile No Chile 25 Ft. o Feb 68 at 500 Ft Marker. 2. Located 300 Ft. N of Rawy 27 No Chile 15 Ft. at 500 Ft. Marker. 8 Mar 68 1...Located 500 Ft.from. Center Linc No Chile No Chile 20 Ft. May 70 and 1500 Pt from end of 1"w 95 2. Located 1100 Ft from Center Lir No Chge J-- 16 Ft and

Benchmark fragment-based 1H, 13C, 15N and 17O chemical shift predictions in molecular crystals†

PubMed Central

Hartman, Joshua D.; Kudla, Ryan A.; Day, Graeme M.; Mueller, Leonard J.; Beran, Gregory J. O.

2016-01-01

The performance of fragment-based ab initio 1H, 13C, 15N and 17O chemical shift predictions is assessed against experimental NMR chemical shift data in four benchmark sets of molecular crystals. Employing a variety of commonly used density functionals (PBE0, B3LYP, TPSSh, OPBE, PBE, TPSS), we explore the relative performance of cluster, two-body fragment, and combined cluster/fragment models. The hybrid density functionals (PBE0, B3LYP and TPSSh) generally out-perform their generalized gradient approximation (GGA)-based counterparts. 1H, 13C, 15N, and 17O isotropic chemical shifts can be predicted with root-mean-square errors of 0.3, 1.5, 4.2, and 9.8 ppm, respectively, using a computationally inexpensive electrostatically embedded two-body PBE0 fragment model. Oxygen chemical shieldings prove particularly sensitive to local many-body effects, and using a combined cluster/fragment model instead of the simple two-body fragment model decreases the root-mean-square errors to 7.6 ppm. These fragment-based model errors compare favorably with GIPAW PBE ones of 0.4, 2.2, 5.4, and 7.2 ppm for the same 1H, 13C, 15N, and 17O test sets. Using these benchmark calculations, a set of recommended linear regression parameters for mapping between calculated chemical shieldings and observed chemical shifts are provided and their robustness assessed using statistical cross-validation. We demonstrate the utility of these approaches and the reported scaling parameters on applications to 9-tertbutyl anthracene, several histidine co-crystals, benzoic acid and the C-nitrosoarene SnCl2(CH3)2(NODMA)2. PMID:27431490

Benchmark fragment-based (1)H, (13)C, (15)N and (17)O chemical shift predictions in molecular crystals.

PubMed

Hartman, Joshua D; Kudla, Ryan A; Day, Graeme M; Mueller, Leonard J; Beran, Gregory J O

2016-08-21

The performance of fragment-based ab initio(1)H, (13)C, (15)N and (17)O chemical shift predictions is assessed against experimental NMR chemical shift data in four benchmark sets of molecular crystals. Employing a variety of commonly used density functionals (PBE0, B3LYP, TPSSh, OPBE, PBE, TPSS), we explore the relative performance of cluster, two-body fragment, and combined cluster/fragment models. The hybrid density functionals (PBE0, B3LYP and TPSSh) generally out-perform their generalized gradient approximation (GGA)-based counterparts. (1)H, (13)C, (15)N, and (17)O isotropic chemical shifts can be predicted with root-mean-square errors of 0.3, 1.5, 4.2, and 9.8 ppm, respectively, using a computationally inexpensive electrostatically embedded two-body PBE0 fragment model. Oxygen chemical shieldings prove particularly sensitive to local many-body effects, and using a combined cluster/fragment model instead of the simple two-body fragment model decreases the root-mean-square errors to 7.6 ppm. These fragment-based model errors compare favorably with GIPAW PBE ones of 0.4, 2.2, 5.4, and 7.2 ppm for the same (1)H, (13)C, (15)N, and (17)O test sets. Using these benchmark calculations, a set of recommended linear regression parameters for mapping between calculated chemical shieldings and observed chemical shifts are provided and their robustness assessed using statistical cross-validation. We demonstrate the utility of these approaches and the reported scaling parameters on applications to 9-tert-butyl anthracene, several histidine co-crystals, benzoic acid and the C-nitrosoarene SnCl2(CH3)2(NODMA)2.

Electro-Spark Deposited Coatings for Replacement of Chrome Electroplating

DTIC Science & Technology

2005-06-01

2.6 0.4 2.2 Thickness uniformity (A-F) 2.8/0.8 2.8/0.8 6.3/0 6.5/0.4 2 to 0 3.9/0.4 Coating integrity (A-F) A A- F C - D A- Defects/mm F D + F D + F B...or width of the wear scar (cm), h is the height or depth of the wear scar (cm), and c is the circumference of the wear scar (cm) where c = "rrd, and d ...inerS4C *2 Panelb MHC583010 -,,IN 3 4853 0.42 roiness 1)N32-15m x c -e sca. 3) &wN x Deb 1nQ withn sar Dein HxW 1).057n*~ 3)211200 12 ve 2 Panl 2 EJC .5 D

Assessing Microbial Activity in Marcellus Shale Hydraulic Fracturing Fluids

NASA Astrophysics Data System (ADS)

Wishart, J. R.; Morono, Y.; Itoh, M.; Ijiri, A.; Hoshino, T.; Inagaki, F.; Verba, C.; Torres, M. E.; Colwell, F. S.

2014-12-01

Hydraulic fracturing (HF) produces millions of gallons of waste fluid which contains a microbial community adapted to harsh conditions such as high temperatures, high salinities and the presence of heavy metals and radionuclides. Here we present evidence for microbial activity in HF production fluids. Fluids collected from a Marcellus shale HF well were supplemented with 13C-labeled carbon sources and 15N-labeled ammonium at 25°C under aerobic or anaerobic conditions. Samples were analyzed for 13C and 15N incorporation at sub-micrometer scale by ion imaging with the JAMSTEC NanoSIMS to determine percent carbon and nitrogen assimilation in individual cells. Headspace CO2 and CH4 were analyzed for 13C enrichment using irm-GC/MS. At 32 days incubation carbon assimilation was observed in samples containing 1 mM 13C-labeled glucose under aerobic and anaerobic conditions with a maximum of 10.4 and 6.5% total carbon, respectively. Nitrogen assimilation of 15N ammonium observed in these samples were 0.3 and 0.8% of total nitrogen, respectively. Head space gas analysis showed 13C enrichment in CH4 in anaerobic samples incubated with 1mM 13C-labeled bicarbonate (2227 ‰) or methanol (98943 ‰). Lesser 13C enrichment of CO2 was observed in anaerobic samples containing 1 mM 13C-labeled acetate (13.7 ‰), methanol (29.9 ‰) or glucose (85.4 ‰). These results indicate metabolic activity and diversity in microbial communities present in HF flowback fluids. The assimilation of 13C-labeled glucose demonstrates the production of biomass, a critical part of cell replication. The production of 13CO2 and 13CH4 demonstrate microbial metabolism in the forms of respiration and methanogenesis, respectively. Methanogenesis additionally indicates the presence of an active archaeal community. This research shows that HF production fluid chemistry does not entirely inhibit microbial activity or growth and encourages further research regarding biogeochemical processes occurring in Marcellus shale HF wells. Biogeochemical activity may impact the efficacy of HF and natural gas production as well as the chemistry of produced fluids which have become an environmental and public health concern.

Toward structural dynamics: protein motions viewed by chemical shift modulations and direct detection of C'N multiple-quantum relaxation.

PubMed

Mori, Mirko; Kateb, Fatiha; Bodenhausen, Geoffrey; Piccioli, Mario; Abergel, Daniel

2010-03-17

Multiple quantum relaxation in proteins reveals unexpected relationships between correlated or anti-correlated conformational backbone dynamics in alpha-helices or beta-sheets. The contributions of conformational exchange to the relaxation rates of C'N coherences (i.e., double- and zero-quantum coherences involving backbone carbonyl (13)C' and neighboring amide (15)N nuclei) depend on the kinetics of slow exchange processes, as well as on the populations of the conformations and chemical shift differences of (13)C' and (15)N nuclei. The relaxation rates of C'N coherences, which reflect concerted fluctuations due to slow chemical shift modulations (CSMs), were determined by direct (13)C detection in diamagnetic and paramagnetic proteins. In well-folded proteins such as lanthanide-substituted calbindin (CaLnCb), copper,zinc superoxide dismutase (Cu,Zn SOD), and matrix metalloproteinase (MMP12), slow conformational exchange occurs along the entire backbone. Our observations demonstrate that relaxation rates of C'N coherences arising from slow backbone dynamics have positive signs (characteristic of correlated fluctuations) in beta-sheets and negative signs (characteristic of anti-correlated fluctuations) in alpha-helices. This extends the prospects of structure-dynamics relationships to slow time scales that are relevant for protein function and enzymatic activity.

Carbon and nitrogen isotopic compositions of particulate organic matter in four large river systems across the United States

USGS Publications Warehouse

Kendall, C.; Silva, S.R.; Kelly, V.J.

2001-01-01

Riverine particulate organic matter (POM) samples were collected bi-weekly to monthly from 40 sites in the Mississippi, Colorado, Rio Grande, and Columbia River Basins (USA) in 1996-97 and analysed for carbon and nitrogen stable isotopic compositions. These isotopic compositions and C : N ratios were used to identify four endmember sources of POM: Plankton, fresh terrestrial plant material, aquatic plants, and soil organic material. This large-scale study also incorporated ancillary chemical and hydrologic data to refine and extend the interpretations of POM sources beyond the source characterizations that could be done solely with isotopic and elemental ratios. The ancillary data were especially useful for differentiating between seasonal changes in POM source materials and the effects of local nutrient sources and in-stream biogeochemical processes. Average values of ??13 C and C : N for all four river systems suggested that plankton is the dominant source of POM in these rivers, with higher percentages of plankton downstream of reservoirs. Although the temporal patterns in some rivers are complex, the low ??13C and C : N values in spring and summer probably indicate plankton blooms, whereas relatively elevated values in fall and winter are consistent with greater proportions of decaying aquatic vegetation and/or terrestrial material. Seasonal shifts in the ??13C of POM when the C : N remains relatively constant probably indicate changes in the relative rates of photosynthesis and respiration. Periodic inputs of plant detritus are suggested by C : N ratios >15, principally on the Columbia and Ohio Rivers. The ??15N and ??13C also reflect the importance of internal and external sources of dissolved carbon and nitrogen, and the degree of in-stream processing. Elevated ??15N values at some sites probably reflect inputs from sewage and/or animal waste. This information on the spatial and temporal variation in sources of POM in four major river systems should prove useful in future food web and nutrient transport studies.

Delta(13)C, delta(15)N and delta(2)H isotope ratio mass spectrometry of ephedrine and pseudoephedrine: application to methylamphetamine profiling.

PubMed

Collins, Michael; Cawley, Adam T; Heagney, Aaron C; Kissane, Luke; Robertson, James; Salouros, Helen

2009-07-01

Conventional chemical profiling of methylamphetamine has been used for many years to determine the synthetic route employed and where possible to identify the precursor chemicals used. In this study stable isotope ratio analysis was investigated as a means of determining the origin of the methylamphetamine precursors, ephedrine and pseudoephedrine. Ephedrine and pseudoephedrine may be prepared industrially by several routes. Results are presented for the stable isotope ratios of carbon (delta(13)C), nitrogen (delta(15)N) and hydrogen (delta(2)H) measured in methylamphetamine samples synthesized from ephedrine and pseudoephedrine of known provenance. It is clear from the results that measurement of the delta(13)C, delta(15)N and delta(2)H stable isotope ratios by elemental analyzer/thermal conversion isotope ratio mass spectrometry (EA/TC-IRMS) in high-purity methylamphetamine samples will allow determination of the synthetic source of the ephedrine or pseudoephedrine precursor as being either of a natural, semi-synthetic, or fully synthetic origin. Copyright (c) 2009 Commonwealth of Australia.

Effects of crop load on distribution and utilization of 13C and 15N and fruit quality for dwarf apple trees.

PubMed

Ding, Ning; Chen, Qian; Zhu, Zhanling; Peng, Ling; Ge, Shunfeng; Jiang, Yuanmao

2017-10-26

In order to define the effects of fruit crop load on the distribution and utilization of carbon and nitrogen in dwarf apple trees, we conducted three crop load levels (High-crop load, 6 fruits per trunk cross-sectional area (cm 2 , TCA)), Medium-crop load (4 fruits cm -2 TCA), Low-crop load (2 fruits cm -2 TCA)) in 2014 and 2015. The results indicated that the 15 N derived from fertilizer (Ndff) values of fruits decreased with the reduction of crop load, but the Ndff values of annual branches, leaves and roots increased. The plant 15 N-urea utilization rates on Medium and Low-crop load were 1.12-1.35 times higher than the High-crop load. With the reduction of crop load, the distribution rate of 13 C and 15 N in fruits was gradually reduced, but in contrast, the distribution of 13 C and 15 N gradually increased in annual branches, leaves and roots. Compared with High-crop load, the Medium and Low-crop load significantly improved fruit quality p < 0.05. Hence, controlling fruit load effectively regulated the distribution of carbon and nitrogen in plants, improved the nitrogen utilization rate and fruit quality. The appropriate crop load level for mature M.26 interstocks apple orchards was deemed to be 4.0 fruits cm -2 TCA.

Regional contamination versus regional dietary differences: Understanding geographic variation in brominated and chlorinated contaminant levels in polar bears

USGS Publications Warehouse

McKinney, M.A.; Letcher, R.J.; Aars, Jon; Born, E.W.; Branigan, M.; Dietz, R.; Evans, T.J.; Gabrielsen, G.W.; Muir, D.C.G.; Peacock, E.; Sonne, C.

2011-01-01

The relative contribution of regional contamination versus dietary differences to geographic variation in polar bear (Ursus maritimus) contaminant levels is unknown. Dietary variation between Alaska Canada, East Greenland, and Svalbard subpopulations was assessed by muscle nitrogen and carbon stable isotope (?? 15N, ?? 13C) and adipose fatty acid (FA) signatures relative to their main prey (ringed seals). Western and southern Hudson Bay signatures were characterized by depleted ?? 15N and ??13C, lower proportions of C20 and C22 monounsaturated FAs and higher proportions of C18 and longer chain polyunsaturated FAs. East Greenland and Svalbard signatures were reversed relative to Hudson Bay. Alaskan ?? 2011 American Chemical Society.

Surface proteins and the formation of biofilms by Staphylococcus aureus.

PubMed

Kim, Sung Joon; Chang, James; Rimal, Binayak; Yang, Hao; Schaefer, Jacob

2018-03-01

Staphylococcus aureus biofilms pose a serious clinical threat as reservoirs for persistent infections. Despite this clinical significance, the composition and mechanism of formation of S. aureus biofilms are unknown. To address these problems, we used solid-state NMR to examine S. aureus (SA113), a strong biofilm-forming strain. We labeled whole cells and cell walls of planktonic cells, young biofilms formed for 12-24h after stationary phase, and more mature biofilms formed for up to 60h after stationary phase. All samples were labeled either by (i) [ 15 N]glycine and l-[1- 13 C]threonine, or in separate experiments, by (ii) l-[2- 13 C, 15 N]leucine. We then measured 13 C- 15 N direct bonds by C{N} rotational-echo double resonance (REDOR). The increase in peptidoglycan stems that have bridges connected to a surface protein was determined directly by a cell-wall double difference (biofilm REDOR difference minus planktonic REDOR difference). This procedure eliminates errors arising from differences in 15 N isotopic enrichments and from the routing of 13 C label from threonine degradation to glycine. For both planktonic cells and the mature biofilm, 20% of pentaglycyl bridges are not cross-linked and are potential surface-protein attachment sites. None of these sites has a surface protein attached in the planktonic cells, but one-fourth have a surface protein attached in the mature biofilm. Moreover, the leucine-label shows that the concentration of β-strands in leucine-rich regions doubles in the mature biofilm. Thus, a primary event in establishing a S. aureus biofilm is extensive decoration of the cell surface with surface proteins that are linked covalently to the cell wall and promote cell-cell adhesion. Copyright © 2017 Elsevier B.V. All rights reserved.

Influence of C-5 substituted cytosine and related nucleoside analogs on the formation of benzo[a]pyrene diol epoxide-dG adducts at CG base pairs of DNA.

PubMed

Guza, Rebecca; Kotandeniya, Delshanee; Murphy, Kristopher; Dissanayake, Thakshila; Lin, Chen; Giambasu, George Madalin; Lad, Rahul R; Wojciechowski, Filip; Amin, Shantu; Sturla, Shana J; Hudson, Robert H E; York, Darrin M; Jankowiak, Ryszard; Jones, Roger; Tretyakova, Natalia Y

2011-05-01

Endogenous 5-methylcytosine ((Me)C) residues are found at all CG dinucleotides of the p53 tumor suppressor gene, including the mutational 'hotspots' for smoking induced lung cancer. (Me)C enhances the reactivity of its base paired guanine towards carcinogenic diolepoxide metabolites of polycyclic aromatic hydrocarbons (PAH) present in cigarette smoke. In the present study, the structural basis for these effects was investigated using a series of unnatural nucleoside analogs and a representative PAH diolepoxide, benzo[a]pyrene diolepoxide (BPDE). Synthetic DNA duplexes derived from a frequently mutated region of the p53 gene (5'-CCCGGCACCC GC[(15)N(3),(13)C(1)-G]TCCGCG-3', + strand) were prepared containing [(15)N(3), (13)C(1)]-guanine opposite unsubstituted cytosine, (Me)C, abasic site, or unnatural nucleobase analogs. Following BPDE treatment and hydrolysis of the modified DNA to 2'-deoxynucleosides, N(2)-BPDE-dG adducts formed at the [(15)N(3), (13)C(1)]-labeled guanine and elsewhere in the sequence were quantified by mass spectrometry. We found that C-5 alkylcytosines and related structural analogs specifically enhance the reactivity of the base paired guanine towards BPDE and modify the diastereomeric composition of N(2)-BPDE-dG adducts. Fluorescence and molecular docking studies revealed that 5-alkylcytosines and unnatural nucleobase analogs with extended aromatic systems facilitate the formation of intercalative BPDE-DNA complexes, placing BPDE in a favorable orientation for nucleophilic attack by the N(2) position of guanine. © The Author(s) 2011. Published by Oxford University Press.

Influence of C-5 substituted cytosine and related nucleoside analogs on the formation of benzo[a]pyrene diol epoxide-dG adducts at CG base pairs of DNA

PubMed Central

Guza, Rebecca; Kotandeniya, Delshanee; Murphy, Kristopher; Dissanayake, Thakshila; Lin, Chen; Giambasu, George Madalin; Lad, Rahul R.; Wojciechowski, Filip; Amin, Shantu; Sturla, Shana J.; Hudson, Robert H.E.; York, Darrin M.; Jankowiak, Ryszard; Jones, Roger; Tretyakova, Natalia Y.

2011-01-01

Endogenous 5-methylcytosine (MeC) residues are found at all CG dinucleotides of the p53 tumor suppressor gene, including the mutational ‘hotspots’ for smoking induced lung cancer. MeC enhances the reactivity of its base paired guanine towards carcinogenic diolepoxide metabolites of polycyclic aromatic hydrocarbons (PAH) present in cigarette smoke. In the present study, the structural basis for these effects was investigated using a series of unnatural nucleoside analogs and a representative PAH diolepoxide, benzo[a]pyrene diolepoxide (BPDE). Synthetic DNA duplexes derived from a frequently mutated region of the p53 gene (5′-CCCGGCACCC GC[15N3,13C1-G]TCCGCG-3′, + strand) were prepared containing [15N3, 13C1]-guanine opposite unsubstituted cytosine, MeC, abasic site, or unnatural nucleobase analogs. Following BPDE treatment and hydrolysis of the modified DNA to 2′-deoxynucleosides, N2-BPDE-dG adducts formed at the [15N3, 13C1]-labeled guanine and elsewhere in the sequence were quantified by mass spectrometry. We found that C-5 alkylcytosines and related structural analogs specifically enhance the reactivity of the base paired guanine towards BPDE and modify the diastereomeric composition of N2-BPDE-dG adducts. Fluorescence and molecular docking studies revealed that 5-alkylcytosines and unnatural nucleobase analogs with extended aromatic systems facilitate the formation of intercalative BPDE–DNA complexes, placing BPDE in a favorable orientation for nucleophilic attack by the N2 position of guanine. PMID:21245046

Carbon molecular sieve membranes on porous composite tubular supports for high performance gas separations

DOE PAGES

Lee, Pyung -Soo; Bhave, Ramesh R.; Nam, Seung -Eun; ...

2016-01-11

Thin carbon molecular sieve membranes (<500 nm) were fabricated inside of long geometry (9 inch) of stainless steel tubes with all welded construction. Alumina intermediate layer on porous stainless steel tube support was used to reduce effective support pore size and to provide a more uniform surface roughness. Novolac phenolic resin solution was then coated on the inside of porous stainless steel tube by slip casting while their viscosities were controlled from 5 centipoises to 30 centipoises. Carbonization was carried out at 700 °C in which thermal stress was minimized and high quality carbon films were prepared. The highest separationmore » performance characteristics were obtained using 20 cP phenolic resin solutions. The fabricated CMSM showed good separation factor for He/N 2 462, CO 2/N 2 97, and O 2/N 2 15.4. As the viscosity of polymer precursor solution was reduced from 20 cP to 15 cP, gas permeance values almost doubled with somewhat lower separation factor He/N 2 156, CO 2/N 2 88, and O 2/N 2 7.7.« less

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 evidence for subduction-related isotopic signatures in the mantle sampled by Panda diamonds.

Expansion of antimonato polyoxovanadates with transition metal complexes: (Co(N3C5H15)2)2[{Co(N3C5H15)2}V15Sb6O42(H2O)]·5H2O and (Ni(N3C5H15)2)2[{Ni(N3C5H15)2}V15Sb6O42(H2O)]·8H2O.

PubMed

Antonova, Elena; Näther, Christian; Kögerler, Paul; Bensch, Wolfgang

2012-02-20

Two new polyoxovanadates (Co(N(3)C(5)H(15))(2))(2)[{Co(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)]·5H(2)O (1) and (Ni(N(3)C(5)H(15))(2))(2)[{Ni(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)]·8H(2)O (2) (N(3)C(5)H(15) = N-(2-aminoethyl)-1,3-propanediamine) were synthesized under solvothermal conditions and structurally characterized. In both structures the [V(15)Sb(6)O(42)(H(2)O)](6-) shell displays the main structural motif, which is strongly related to the {V(18)O(42)} archetype cluster. Both compounds crystallize in the triclinic space group P1 with a = 14.3438(4), b = 16.6471(6), c = 18.9186(6) Å, α = 87.291(3)°, β = 83.340(3)°, γ = 78.890(3)°, and V = 4401.4(2) Å(3) (1) and a = 14.5697(13), b = 15.8523(16), c = 20.2411(18) Å, α = 86.702(11)°, β = 84.957(11)°, γ = 76.941(11)°, and V = 4533.0(7) Å(3) (2). In the structure of 1 the [V(15)Sb(6)O(42)(H(2)O)](6-) cluster anion is bound to a [Co(N(3)C(5)H(15))(2)](2+) complex via a terminal oxygen atom. In the Co(2+)-centered complex, one of the amine ligands coordinates in tridentate mode and the second one in bidentate mode to form a strongly distorted CoN(5)O octahedron. Similarly, in compound 2 an analogous NiN(5)O complex is joined to the [V(15)Sb(6)O(42)(H(2)O)](6-) anion via the same attachment mode. A remarkable difference between the two compounds is the orientation of the noncoordinated propylamine group leading to intermolecular Sb···O contacts in 1 and to Sb···N interactions in 2. In the solid-state lattices of 1 and 2, two additional [M(N(3)C(5)H(15))(2)](2+) complexes act as countercations and are located between the [{M(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)](4-) anions. Between the anions and cations strong N-H···O hydrogen bonds are observed. In both compounds the clusters are stacked along the b axis in an ABAB fashion with cations and water molecules occupying the space between the clusters. Magnetic characterization demonstrates that the Ni(2+) and Co(2+) cations do not significantly couple with the S = 1/2 vanadyl groups. The susceptibility data can be successfully reproduced assuming a distorted ligand field for the Co(2+) ions (1) and an O(h)-symmetric Ni(2+) ligand field (2).

Compound-Specific δ¹⁵N and δ¹³C Analyses of Amino Acids for Potential Discrimination between Organically and Conventionally Grown Wheat.

PubMed

Paolini, Mauro; Ziller, Luca; Laursen, Kristian Holst; Husted, Søren; Camin, Federica

2015-07-01

We present a study deploying compound-specific nitrogen and carbon isotope analysis of amino acids to discriminate between organically and conventionally grown plants. We focused on grain samples of common wheat and durum wheat grown using synthetic nitrogen fertilizers, animal manures, or green manures from nitrogen-fixing legumes. The measurement of amino acid δ(15)N and δ(13)C values, after protein hydrolysis and derivatization, was carried out using gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS). Our results demonstrated that δ(13)C of glutamic acid and glutamine in particular, but also the combination of δ(15)N and δ(13)C of 10 amino acids, can improve the discrimination between conventional and organic wheat compared to stable isotope bulk tissue analysis. We concluded that compound-specific stable isotope analysis of amino acids represents a novel analytical tool with the potential to support and improve the certification and control procedures in the organic sector.

Nitrogen isotopes suggest a change in nitrogen dynamics between the Late Pleistocene and modern time in Yukon, Canada

PubMed Central

Longstaffe, Fred J.; Zazula, Grant

2018-01-01

A magnificent repository of Late Pleistocene terrestrial megafauna fossils is contained in ice-rich loess deposits of Alaska and Yukon, collectively eastern Beringia. The stable carbon (δ13C) and nitrogen (δ15N) isotope compositions of bone collagen from these fossils are routinely used to determine paleodiet and reconstruct the paleoecosystem. This approach requires consideration of changes in C- and N-isotope dynamics over time and their effects on the terrestrial vegetation isotopic baseline. To test for such changes between the Late Pleistocene and modern time, we compared δ13C and δ15N for vegetation and bone collagen and structural carbonate of some modern, Yukon, arctic ground squirrels with vegetation and bones from Late Pleistocene fossil arctic ground squirrel nests preserved in Yukon loess deposits. The isotopic discrimination between arctic ground squirrel bone collagen and their diet was measured using modern samples, as were isotopic changes during plant decomposition; Over-wintering decomposition of typical vegetation following senescence resulted in a minor change (~0–1 ‰) in δ13C of modern Yukon grasses. A major change (~2–10 ‰) in δ15N was measured for decomposing Yukon grasses thinly covered by loess. As expected, the collagen-diet C-isotope discrimination measured for modern samples confirms that modern vegetation δ13C is a suitable proxy for the Late Pleistocene vegetation in Yukon Territory, after correction for the Suess effect. The N-isotope composition of vegetation from the fossil arctic ground squirrel nests, however, is determined to be ~2.8 ‰ higher than modern grasslands in the region, after correction for decomposition effects. This result suggests a change in N dynamics in this region between the Late Pleistocene and modern time. PMID:29447202

Nitrogen isotopes suggest a change in nitrogen dynamics between the Late Pleistocene and modern time in Yukon, Canada.

PubMed

Tahmasebi, Farnoush; Longstaffe, Fred J; Zazula, Grant

2018-01-01

A magnificent repository of Late Pleistocene terrestrial megafauna fossils is contained in ice-rich loess deposits of Alaska and Yukon, collectively eastern Beringia. The stable carbon (δ13C) and nitrogen (δ15N) isotope compositions of bone collagen from these fossils are routinely used to determine paleodiet and reconstruct the paleoecosystem. This approach requires consideration of changes in C- and N-isotope dynamics over time and their effects on the terrestrial vegetation isotopic baseline. To test for such changes between the Late Pleistocene and modern time, we compared δ13C and δ15N for vegetation and bone collagen and structural carbonate of some modern, Yukon, arctic ground squirrels with vegetation and bones from Late Pleistocene fossil arctic ground squirrel nests preserved in Yukon loess deposits. The isotopic discrimination between arctic ground squirrel bone collagen and their diet was measured using modern samples, as were isotopic changes during plant decomposition; Over-wintering decomposition of typical vegetation following senescence resulted in a minor change (~0-1 ‰) in δ13C of modern Yukon grasses. A major change (~2-10 ‰) in δ15N was measured for decomposing Yukon grasses thinly covered by loess. As expected, the collagen-diet C-isotope discrimination measured for modern samples confirms that modern vegetation δ13C is a suitable proxy for the Late Pleistocene vegetation in Yukon Territory, after correction for the Suess effect. The N-isotope composition of vegetation from the fossil arctic ground squirrel nests, however, is determined to be ~2.8 ‰ higher than modern grasslands in the region, after correction for decomposition effects. This result suggests a change in N dynamics in this region between the Late Pleistocene and modern time.

Disentangling effects of growth and nutritional status on seabird stable isotope ratios

USGS Publications Warehouse

Sears, J.; Hatch, Shyla A.; O'Brien, D. M.

2009-01-01

A growing number of studies suggest that an individual's physiology affects its carbon and nitrogen stable isotope signatures, obscuring a signal often assumed to be only a reflection of diet and foraging location. We examined effects of growth and moderate food restriction on red blood cell (RBC) and feather ??15N and ??13C in rhinoceros auklet chicks (Cerorhinca monocerata), a piscivorous seabird. Chicks were reared in captivity and fed either control (75 g/day; n = 7) or ~40% restricted (40 g/day; n = 6) amounts of high quality forage fish. We quantified effects of growth on isotopic fractionation by comparing ??15N and ??13C in control chicks to those of captive, non-growing subadult auklets (n = 11) fed the same diet. To estimate natural levels of isotopic variation, we also collected blood from a random sample of free-living rhinoceros auklet adults and chicks in the Gulf of Alaska (n = 15 for each), as well as adult feather samples (n = 13). In the captive experiment, moderate food restriction caused significant depletion in ??15N of both RBCs and feathers in treatment chicks compared to control chicks. Growth also induced depletion in RBC ??15N, with chicks exhibiting lower ??15N when they were growing the fastest. As growth slowed, ??15N increased, resulting in an overall pattern of enrichment over the course of the nestling period. Combined effects of growth and restriction depleted ??15N in chick RBCs by 0.92???. We propose that increased nitrogen-use efficiency is responsible for 15N depletion in both growing and food-restricted chicks. ??15N values in RBCs of free-ranging auklets fell within a range of only 1.03???, while feather ??15N varied widely. Together, our captive and field results suggest that both growth and moderate food restriction can affect stable isotope ratios in an ecologically meaningful way in RBCs although not feathers due to greater natural variability in this tissue. ?? 2008 Springer-Verlag.

δ13C and d15N in the endangered Kemp’s ridley sea turtle Lepidochelys kempii after the Deepwater Horizon oil spill

USGS Publications Warehouse

Reich, Kimberly J.; López-Castro, Melania C.; Shaver, Donna J.; Iseton, Claire; Hart, Kristen M.; Hooper, Michael J.; Schmitt, Christopher J.

2017-01-01

The Deepwater Horizon explosion in April 2010 and subsequent oil spill released 3.19 × 106 barrels (5.07 × 108 L) of MC252 crude oil into important foraging areas of the endangered Kemp’s ridley sea turtle Lepidochelys kempii (Lk) in the northern Gulf of Mexico (GoM). We measured δ13C and δ15N in scute biopsy samples from 33 Lk nesting in Texas during 2010–-12. Of these, 27 were equipped with satellite transmitters and were tracked to traditional foraging areas in the northern GoM after the spill. Differences in δ13C between the oldest and newest scute layers from 2010 nesters were not significantly different, but δ13C in the newest layers from 2011 and 2012 nesters was significantly lower compared to 2010. δ15N differences were not statistically significant. Collectively, the stable isotope and tracking data indicate that the lower δ13C values reflect the incorporation of oil rather than changes in diet or foraging area. Discriminant analysis indicated that 51.5% of the turtles sampled had isotope signatures indicating oil exposure. Growth of the Lk population slowed in the years following the spill. The involvement of oil exposure in recent population trends is unknown, but long-term effects may not be evident for many years. Our results indicate that C isotope signatures in scutes may be useful biomarkers of sea turtle exposure to oil.

Stable isotope composition (δ(13)C and δ(15)N values) of slime molds: placing bacterivorous soil protozoans in the food web context.

PubMed

Tiunov, Alexei V; Semenina, Eugenia E; Aleksandrova, Alina V; Tsurikov, Sergey M; Anichkin, Alexander E; Novozhilov, Yuri K

2015-08-30

Data on the bulk stable isotope composition of soil bacteria and bacterivorous soil animals are required to estimate the nutrient and energy fluxes via bacterial channels within detrital food webs. We measured the isotopic composition of slime molds (Myxogastria, Amoebozoa), a group of soil protozoans forming macroscopic spore-bearing fruiting bodies. An analysis of largely bacterivorous slime molds can provide information on the bulk stable isotope composition of soil bacteria. Fruiting bodies of slime molds were collected in a monsoon tropical forest of Cat Tien National Park, Vietnam, and analyzed by continuous-flow isotope ratio mass spectrometry. Prior to stable isotope analysis, carbonates were removed from a subset of samples by acidification. To estimate the trophic position of slime molds, their δ(13) C and δ(15) N values were compared with those of plant debris, soil, microbial destructors (litter-decomposing, humus-decomposing, and ectomycorrhizal fungi) and members of higher trophic levels (oribatid mites, termites, predatory macroinvertebrates). Eight species of slime molds represented by at least three independent samples were 3-6‰ enriched in (13) C and (15) N relative to plant litter. A small but significant difference in the δ(13) C and δ(15) N values suggests that different species of myxomycetes can differ in feeding behavior. The slime molds were enriched in (15) N compared with litter-decomposing fungi, and depleted in (15) N compared with mycorrhizal or humus-decomposing fungi. Slime mold sporocarps and plasmodia largely overlapped with oribatid mites in the isotopic bi-plot, but were depleted in (15) N compared with predatory invertebrates and humiphagous termites. A comparison with reference groups of soil organisms suggests strong trophic links of slime molds to saprotrophic microorganisms which decompose plant litter, but not to humus-decomposing microorganisms or to mycorrhizal fungi. Under the assumption that slime molds are primarily feeding on bacteria, the isotopic similarity of slime molds and mycophagous soil animals indicates that saprotrophic soil bacteria and fungi are similar in bulk isotopic composition. Copyright © 2015 John Wiley & Sons, Ltd.

The Great Irish Famine: Identifying Starvation in the Tissues of Victims Using Stable Isotope Analysis of Bone and Incremental Dentine Collagen

PubMed Central

Montgomery, Janet

2016-01-01

The major components of human diet both past and present may be estimated by measuring the carbon and nitrogen isotope ratios (δ13C and δ15N) of the collagenous proteins in bone and tooth dentine. However, the results from these two tissues differ substantially: bone collagen records a multi-year average whilst primary dentine records and retains time-bound isotope ratios deriving from the period of tooth development. Recent studies harnessing a sub-annual temporal sampling resolution have shed new light on the individual dietary histories of our ancestors by identifying unexpected radical short-term dietary changes, the duration of breastfeeding and migration where dietary change occurs, and by raising questions regarding factors other than diet that may impact on δ13C and δ15N values. Here we show that the dentine δ13C and δ15N profiles of workhouse inmates dating from the Great Irish Famine of the 19th century not only record the expected dietary change from C3 potatoes to C4 maize, but when used together they also document prolonged nutritional and other physiological stress resulting from insufficient sustenance. In the adults, the influence of the maize-based diet is seen in the δ13C difference between dentine (formed in childhood) and rib (representing an average from the last few years of life). The demonstrated effects of stress on the δ13C and δ15N values will have an impact on the interpretations of diet in past populations even in slow-turnover tissues such as compact bone. This technique also has applicability in the investigation of modern children subject to nutritional distress where hair and nails are unavailable or do not record an adequate period of time. PMID:27508412

Nearshore energy subsidies support Lake Michigan fishes and invertebrates following major changes in food web structure

USGS Publications Warehouse

Turschak, Benjamin A; Bunnell, David B.; Czesny, Sergiusz J.; Höök, Tomas O.; Janssen, John; Warner, David M.; Bootsma, Harvey A

2014-01-01

Aquatic food webs that incorporate multiple energy channels (e.g. nearshore benthic or pelagic) with varying productivity and turnover rates convey stability to biological communities by providing multiple independent energy sources. Within the Lake Michigan food web, invasive dreissenid mussels have caused rapid changes to food web structure and potentially altered the channels through which consumers acquire energy. We used stable C and N isotopes to determine how Lake Michigan food web structure has changed in the past decade, coincident with the expansion of dreissenid mussels, decreased pelagic phytoplankton production and increased nearshore benthic algal production. Fish and invertebrate samples collected from sites around Lake Michigan were analyzed to determine taxa-specific 13C:12C (delta 13C) and 15N:14N (delta 15N) ratios. Sampling took place during two distinct periods, 2002-2003 and 2010-2012, that spanned the period of dreissenid expansion, and included nearshore, pelagic and profundal fish and invertebrate taxa. Magnitude and direction of the 13C shift indicated significantly greater reliance upon nearshore benthic energy sources among nearly all fish taxa as well as profundal invertebrates. Although the mechanisms underlying this 13C shift likely varied among species, possible causes include the transport of benthic algal production to offshore waters and an increased reliance on nearshore prey items. Delta 15N shifts were more variable and of smaller magnitude across taxa although declines in delta 15N among some pelagic fishes may indicate a shift to alternative prey resources. Lake Michigan fishes and invertebrates appear to have responded to dreissenid induced changes in nutrient and energy pathways by switching from pelagic to alternative nearshore energy subsidies. Although large shifts in energy allocation (i.e. pelagic to nearshore benthic) resulting from invasive species appear to have affected total production at upper trophic levels, changes in trophic structure and utilization of novel energy pathways may help to stabilize food webs following species invasions.

Accurate measurement of heteronuclear dipolar couplings by phase-alternating R-symmetry (PARS) sequences in magic angle spinning NMR spectroscopy

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

Hou, Guangjin, E-mail: hou@udel.edu, E-mail: tpolenov@udel.edu; Lu, Xingyu, E-mail: luxingyu@udel.edu, E-mail: lexvega@comcast.net; Vega, Alexander J., E-mail: luxingyu@udel.edu, E-mail: lexvega@comcast.net

2014-09-14

We report a Phase-Alternating R-Symmetry (PARS) dipolar recoupling scheme for accurate measurement of heteronuclear {sup 1}H-X (X = {sup 13}C, {sup 15}N, {sup 31}P, etc.) dipolar couplings in MAS NMR experiments. It is an improvement of conventional C- and R-symmetry type DIPSHIFT experiments where, in addition to the dipolar interaction, the {sup 1}H CSA interaction persists and thereby introduces considerable errors in the dipolar measurements. In PARS, phase-shifted RN symmetry pulse blocks applied on the {sup 1}H spins combined with π pulses applied on the X spins at the end of each RN block efficiently suppress the effect from {supmore » 1}H chemical shift anisotropy, while keeping the {sup 1}H-X dipolar couplings intact. Another advantage over conventional DIPSHIFT experiments, which require the signal to be detected in the form of a reduced-intensity Hahn echo, is that the series of π pulses refocuses the X chemical shift and avoids the necessity of echo formation. PARS permits determination of accurate dipolar couplings in a single experiment; it is suitable for a wide range of MAS conditions including both slow and fast MAS frequencies; and it assures dipolar truncation from the remote protons. The performance of PARS is tested on two model systems, [{sup 15}N]-N-acetyl-valine and [U-{sup 13}C,{sup 15}N]-N-formyl-Met-Leu-Phe tripeptide. The application of PARS for site-resolved measurement of accurate {sup 1}H-{sup 15}N dipolar couplings in the context of 3D experiments is presented on U-{sup 13}C,{sup 15}N-enriched dynein light chain protein LC8.« less

Online liquid chromatography-tandem mass spectrometry cyanide determination in blood.

PubMed

Lacroix, C; Saussereau, E; Boulanger, F; Goullé, J P

2011-04-01

An original liquid chromatography-tandem mass spectrometry (LC-MS-MS) method coupled to online extraction has been developed for cyanide determination in blood. A method involving fluorimetric detection after naphthalene-2,3-dicarboxyaldehyde (NDA) complexation by taurine in the presence of cyanide was previously described. Its performance was limited because of the absence of an internal standard (IS). Using cyanide isotope (13)C(15)N as IS allowed quantification in MS-MS. After the addition of (13)C(15)N, 25 μL of blood were diluted in water and deproteinized with methanol. Following derivatization with NDA and taurine for 10 min at 4°C, 100 μL was injected into the online LC-MS-MS system. An Oasis HLB was used as an extraction column, and a C18 Atlantis was the analytical column. The chromatographic cycle was performed with an ammonium formate (20 mM, pH 2.8) (solvent A) and acetonitrile/solvent A (90:10, v/v) gradient in 6 min. Detection was performed in negative electrospray ionization mode (ESI(-)) with a Quattro Micro. For quantification, transitions of derivatives formed with CN and (13)C(15)N were monitored, respectively, as follows: 299.3/191.3 and 301.3/193.3. The procedure was fully validated, linear from 26 to 2600 ng/mL with limit of detection of 10 ng/mL. This method, using a small blood sample, is not only simple, but also time saving. The specificity and sensitivity of LC-MS-MS coupled to online extraction and using (13)C(15)N as the IS make this method very suitable for cyanide determination in blood and could be useful in forensic toxicology.

Sum-over-states density functional perturbation theory: Prediction of reliable 13C, 15N, and 17O nuclear magnetic resonance chemical shifts

NASA Astrophysics Data System (ADS)

Olsson, Lars; Cremer, Dieter

1996-11-01

Sum-over-states density functional perturbation theory (SOS-DFPT) has been used to calculate 13C, 15N, and 17O NMR chemical shifts of 20 molecules, for which accurate experimental gas-phase values are available. Compared to Hartree-Fock (HF), SOS-DFPT leads to improved chemical shift values and approaches the degree of accuracy obtained with second order Møller-Plesset perturbation theory (MP2). This is particularly true in the case of 15N chemical shifts where SOS-DFPT performs even better than MP2. Additional improvements of SOS-DFPT chemical shifts can be obtained by empirically correcting diamagnetic and paramagnetic contributions to compensate for deficiencies which are typical of DFT.

Necessity of Removing American Football Uniforms From Humans With Hyperthermia Before Cold-Water Immersion.

PubMed

Miller, Kevin C; Long, Blaine C; Edwards, Jeffrey

2015-12-01

The National Athletic Trainers' Association and the American College of Sports Medicine have recommended removing American football uniforms from athletes with exertional heat stroke before cold-water immersion (CWI) based on the assumption that the uniform impedes rectal temperature (T(rec)) cooling. Few experimental data exist to verify or disprove this assumption and the recommendations. To compare CWI durations, T(rec) cooling rates, thermal sensation, intensity of environmental symptoms, and onset of shivering when hyperthermic participants wore football uniforms during CWI or removed the uniforms immediately before CWI. Crossover study. Laboratory. Eighteen hydrated, physically active men (age = 22 ± 2 years, height = 182.5 ± 6.1 cm, mass = 85.4 ± 13.4 kg, body fat = 11% ± 5%, body surface area = 2.1 ± 0.2 m(2)) volunteered. On 2 days, participants exercised in the heat (approximately 40°C, approximately 40% relative humidity) while wearing a full American football uniform (shoes; crew socks; undergarments; shorts; game pants; undershirt; shoulder pads; jersey; helmet; and padding over the thighs, knees, hips, and tailbone [PADS]) until T(rec) reached 39.5°C. Next, participants immersed themselves in water that was approximately 10°C while wearing either undergarments, shorts, and crew socks (NOpads) or PADS without shoes until Trec reached 38°C. The CWI duration (minutes) and T(rec) cooling rates (°C/min). Participants had similar exercise times (NOpads = 40.8 ± 4.9 minutes, PADS = 43.2 ± 4.1 minutes; t(17) = 2.0, P = .10), hypohydration levels (NOpads = 1.5% ± 0.3%, PADS = 1.6% ± 0.4%; t(17) = 1.3, P = .22), and thermal-sensation ratings (NOpads = 7.2 ± 0.3, PADS = 7.1 ± 0.5; P > .05) before CWI. The CWI duration (median [interquartile range]; NOpads = 6.0 [5.4] minutes, PADS = 7.3 [9.8] minutes; z = 2.3, P = .01) and T(rec) cooling rates (NOpads = 0.28°C/min ± 0.14°C/min, PADS = 0.21°C/min ± 0.11°C/min; t(17) = 2.2, P = .02) differed between uniform conditions. Whereas participants cooled faster in NOpads, we still considered the PADS cooling rate to be acceptable (ie, >0.16°C/min). Therefore, if clinicians experience difficulty removing PADS or CWI treatment is delayed, they may immerse fully equipped hyperthermic football players in CWI and maintain acceptable T(rec) cooling rates. Otherwise, PADS should be removed preimmersion to ensure faster body core temperature cooling.

Performance of intermittent aeration reactor on NH4-N removal from groundwater resources.

PubMed

Khanitchaidecha, W; Nakamura, T; Sumino, T; Kazama, F

2010-01-01

To study the effect of intermittent aeration period on ammonium-nitrogen (NH4-N) removal from groundwater resources, synthetic groundwater was prepared and three reactors were operated under different conditions--"reactor A" under continuous aeration, "reactor B" under 6 h intermittent aeration, and "reactor C" under 2 h intermittent aeration. To facilitate denitrification simultaneously with nitrification, "acetate" was added as an external carbon source with step-wise increase from 0.5 to 1.5 C/N ratio, where C stands for total carbon content in the system, and N for NH4-N concentration in the synthetic groundwater. Results show that complete NH4-N removal was obtained in "reactor B" and "reactor C" at 1.3 and 1.5 C/N ratio respectively; and partial NH4-N removal in "reactor A". These results suggest that intermittent aeration at longer interval could enhance the reactor performance on NH4-N removal in terms of efficiency and low external carbon requirement. Because of consumption of internal carbon by the process, less amount of external carbon is required. Further increase in carbon in a form of acetate (1.5 to 2.5 C/N ratios) increases removal rate (represented by reaction rate coefficient (k) of kinetic equation) as well as occurrence of free cells. It suggests that the operating condition at reactor B with 1.3 C/N ratio is more appropriate for long-term operation at a pilot-scale.

(1)H, (13)C, (15)N backbone and side-chain resonance assignment of Nostoc sp. C139A variant of the heme-nitric oxide/oxygen binding (H-NOX) domain.

PubMed

Alexandropoulos, Ioannis I; Argyriou, Aikaterini I; Marousis, Kostas D; Topouzis, Stavros; Papapetropoulos, Andreas; Spyroulias, Georgios A

2016-10-01

The H-NOX (Heme-nitric oxide/oxygen binding) domain is conserved across eukaryotes and bacteria. In human soluble guanylyl cyclase (sGC) the H-NOX domain functions as a sensor for the gaseous signaling agent nitric oxide (NO). sGC contains the heme-binding H-NOX domain at its N-terminus, which regulates the catalytic site contained within the C-terminal end of the enzyme catalyzing the conversion of GTP (guanosine 5'-triphosphate) to GMP (guanylyl monophosphate). Here, we present the backbone and side-chain assignments of the (1)H, (13)C and (15)N resonances of the 183-residue H-NOX domain from Nostoc sp. through solution NMR.

Phosphorus-31, sup 15 N, and sup 13 C NMR of glyphosate: Comparison of pH titrations to the herbicidal dead-end complex with 5-enolpyruvoylshikimate-3-phosphate synthase

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

Castellino, S.; Leo, G.C.; Sammons, R.D.

1989-05-02

The herbicidal dead-end ternary complex (E{sup S3P}{sub Glyph}) of glyphosate (N-(phosphonomethyl)glycine) with 5-enolpyruvoylshikimate-3-phosphate synthase (EPSPS) and the substrate shikimate 3-phosphate (S3P) has been characterized by {sup 31}P, {sup 15}N, and {sup 13}C NMR. The NMR spectra of EPSPS-bound glyphosate show unique chemical shifts ({delta}) for each of the three nuclei. By {sup 31}P NMR, glyphosate in the dead-end complex is a distinct species 3.5 ppm downfield from free glyphosate. The {sup 13}C signal of glyphosate in the dead-end complex is shifted 4 ppm downfield from that of free glyphosate. The {sup 15}N signal for glyphosate (99%) in the dead-end complexmore » is 5 ppm further downfield than that of any free zwitterionic species and 10 ppm downfield from that of the average free species at pH 10.1. The structures of each ionic state of glyphosate are modeled with force field calculations by using MacroModel. A correlation is made for the {sup 31}P {delta} and the C-P-O bond angle, and the {sup 13}C and {sup 15}N {delta} values are postulated to be related to C-C-O and C-N-C bond angles, respectively. The downfield {sup 31}P chemical shift perturbation for S3P in the EPSPS binary complex is consistent with ionization of the 3-phosphate of S3P upon binding. Comparison with the S3P {sup 31}P {delta} vs pH titration curve specifies predominantly the dianion of the 3-phosphate in the E{sup S3P} binary complex, while the E{sup S3P}{sub Glyph} complex indicates net protonation at the 3-phosphate. Chemical shift perturbations of this latter type may be explained by changes in the O-P-O bond angle.« less

Passive aeration composting of chicken litter: effects of aeration pipe orientation and perforation size on losses of compost elements.

PubMed

Ogunwande, Gbolabo A; Osunade, James A

2011-01-01

A passive aeration composting study was undertaken to investigate the effects of aeration pipe orientation (PO) and perforation size (PS) on some physico-chemical properties of chicken litter (chicken manure + sawdust) during composting. The experimental set up was a two-factor completely randomised block design with two pipe orientations: horizontal (Ho) and vertical (Ve), and three perforation sizes: 15, 25 and 35 mm diameter. The properties monitored during composting were pile temperature, moisture content (MC), pH, electrical conductivity (EC), total carbon (C(T)), total nitrogen (N(T)) and total phosphorus (P(T)). Moisture level in the piles was periodically replenished to 60% for efficient microbial activities. The results of the study showed that optimum composting conditions (thermophilic temperatures and sanitation requirements) were attained in all the piles. During composting, both PO and PS significantly affected pile temperature, moisture level, pH, C(T) loss and P(T) gain. EC was only affected by PO while N(T) was affected by PS. Neither PO nor PS had a significant effect on the C:N ratio. A vertical pipe was effective for uniform air distribution, hence, uniform composting rate within the composting pile. The final values showed that PO of Ve and PS of 35 mm diameter resulted in the least loss in N(T). The PO of Ho was as effective as Ve in the conservation of C(T) and P(T). Similarly, the three PSs were equally effective in the conservation of C(T) and P(T). In conclusion, the combined effects of PO and PS showed that treatments Ve35 and Ve15 were the most effective in minimizing N(T) loss. Copyright © 2010 Elsevier Ltd. All rights reserved.

A priori predictions of the rotational constants for HC13N, HC15N, C5O

NASA Technical Reports Server (NTRS)

DeFrees, D. J.; McLean, A. D.

1989-01-01

Ab initio molecular orbital theory is used to estimate the rotational constant for several carbon-chain molecules that are candidates for discovery in interstellar space. These estimated rotational constants can be used in laboratory or astronomical searches for the molecules. The rotational constant for HC13N is estimated to be 0.1073 +/- 0.0002 GHz and its dipole moment 5.4 D. The rotational constant for HC15N is estimated to be 0.0724 GHz, with a somewhat larger uncertainty. The rotational constant of C5O is estimated to be 1.360 +/- 2% GHz and its dipole moment 4.4. D.

(DURIP) MIMO Radar Testbed for Waveform Adaptive Sensing Research

DTIC Science & Technology

2015-06-17

OH 43210 -1016 31-Aug...Ohio State University Columbus, OH Foreword Microwave radar systems are crucial components of any standoff sensor system due to their all-weather...976LP 3E E N 1 R D 2 R E F 3 V R X 4 HV 5 N/C1 6 N/C2 7 N/C3 8 N /C 4 9 N /C 5 10 V R 11 N /C 6 12 N/C7 13 N/ C8 14 VDD 15 N/C9 16 GND_2 17 C 9 10uF C

A multi‐isotope investigation of diet and subsistence amongst island and mainland populations from early medieval western Britain

PubMed Central

Lamb, Angela L.; Chenery, Carolyn A.; Evans, Jane A.

2016-01-01

Abstract Objectives This is the first investigation of dietary practices amongst multiple early medieval populations (AD 500–1000) from Wales and the Isle of Man using carbon, nitrogen, and sulphur isotope analysis. The analysis will illuminate similarities or differences between the diets and subsistence strategies of populations occupying different geographical regions, specifically those living in marginal coastal regions in comparison to inland populations well‐connected to ecclesiastical centres and high‐status settlements. Materials and Methods One hundred and two human skeletons were sampled for carbon and nitrogen isotope analysis, and 69 human skeletons were sampled for sulphur isotope analysis from nine cemetery sites from western Britain (Isle of Man = 3, southwest Wales = 4, southeast Wales = 2). Thirteen faunal skeletons from St Patrick's Chapel (southwest Wales) were sampled for carbon, nitrogen, and sulphur isotope analysis. Results Human δ13C values range from −19.4‰ to −21.2‰ (δ13C mean=−20.4 ±0.4‰, 1σ, n = 86), and δ15N values range from 9.1‰ to 13.8‰ (δ15N mean = 10.8 ± 0.9‰, 1σ, n = 86). δ34S values range from 1.2‰ to 18.4‰ (δ34S mean = 11.6 ± 4.5‰, 1σ, n = 66). Significant differences were noted between the mean δ13C, δ15N and δ34S values according to geographic region: Isle of Man (δ13C = −20.7 ± 0.4‰, δ15N = 11.4 ±0.6‰, n = 13/86; δ34S mean = 17.1 ±0.6, n = 4/66), southwest Wales (δ13C = −20.5 ± 0.4‰, δ15N = 11.0 ±1‰, n = 32/86; δ34S = 16.1 ± 2.1, n = 21/66), and southeast Wales (δ13C =−20.3 ±0.4‰, δ15N = 10.4 ±0.7‰, n = 41/86; δ34S= 8.8 ±3‰, n = 41/66). Faunal δ13C values range from −23.1‰ to −21.2‰ (δ13C mean= −22.1 ±0.5‰, 1σ, n = 13), and δ15N values range from 6.3‰ to 9.8‰ (δ15N mean = 7.3 ± 1.1‰, 1σ, n = 13). δ34S values range from 4.7‰ to 18.4‰ (δ34S mean= 16.3 ± 3.6‰, 1σ, n = 13). Conclusions The data reveal a reliance on terrestrial protein, however differences are observed between the resource consumption of populations from southwest Wales and the Isle of Man in comparison to the populations from southeast Wales. Populations from the west coast have a marine sulphur signature that reflects their coastal proximity and may also include a reliance on seaweed as a fertiliser/food source. Populations in the southeast were connected to ecclesiastical centres and high‐status settlements and had access to inland‐grown produce. The data add support to the suggestion that δ34S can be used as a mobility indicator. PMID:27858981

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

PubMed

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

2002-12-18

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

Compound-Specific Amino Acid Isotopic Analysis of Benthic Food Webs in the Chukchi Sea

NASA Astrophysics Data System (ADS)

Zhang, M.; Cooper, L. W.; Biasatti, D. M.; Grebmeier, J. M.

2014-12-01

The Chukchi Sea is known for locally high standing stocks of benthic macrofauna and strong coupling between pelagic-benthic components of the ecosystem. However, benthic food structure is not fully understood, due to varied sources of particulate organic matter (POM) and the high diversity of benthic invertebrates. We provide the first demonstration of the application of compound-specific amino acid isotope analysis to study the dietary sources and trophic structure for this Arctic marginal sea. About 20 stations in Chukchi Sea were sampled during cruises in August of 2012 and 2013. At each station, phytoplankton, POM and benthic fauna were collected, processed and analyzed using GC-C-IRMS (gas chromatography-combustion-isotope ratio mass spectrometry). Among benthic fauna, dominant species included the following taxonomic groups: Ophiuroidea, Amphipoda, Polychaeta, Gastropoda, Bivalvia, and Cnidaria. The benthic fauna showed similar patterns of individual amino acid δ13C, with glycine the most enriched in 13C and leucine the most depleted in 13C. Specific amino acids including phenylalanine showed spatial variability in δ13C and δ15N values within the sampled area, indicating contributions of different dietary sources including phytoplankton, sea ice algae, benthic algae and terrestrial organic materials. δ15N values of individual amino acids such as the difference between glutamic acid and phenylalanine, i.e. Δ15Nglu-phe (δ15Nglu - δ15Nphe), were also used to identify trophic levels of benthic invertebrates relative to estimates available from bulk δ15N values. These data will ultimately be used to evaluate the spatial variability of organic carbon sources and trophic level interactions of dominant benthic species in the Chukchi Sea.

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

NASA Astrophysics Data System (ADS)

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

2002-12-01

Extrapolations into ancient biomes make many assumptions and inferences regarding life modes and environmental habitat. While definition of a stromatolite as an extinct microbial biome by petrographic analysis is promising, Life interacts with is environment, actively manipulating energy flow across chemical disequilibria gradients, harvesting energy crucial for physiological maintenance and reproduction. Such structuring of communities in turn, leaves specific chemical/isotopic imprints related to physiological processes of prokaryotic communities specific to each oxidation/redox horizon. We examine stable isotopic d13C signals (d13C and d15N) as potential biomarkers reflecting bacterial physiology and microbial community nutrient-energy dynamics. While isotopes may reveal ancient chemical structuring of microbial mats, we also turn to invoking viral lysing of bacterial hosts in nutrient cycling within modern extreme environments as well as ancient stromatic structures of early Earth. Our records of d13C indicate extreme enrichment(-12%) for Corg in our extant mat due to CO2 limitation across a hypersaline diffusive barrier at the mat's surface. d15N is lowest at the mat's surface (indicating N2- fixation) where nitrogen- fixing cyanobacteria Microcoleus sp. are present . Viruses are extremely abundant in the microbial mat, exceeding bacterial abundances by a factor of ten. The ratio of viruses to bacteria was very high (VBR = 39 ñ 10) compared with abundances in marine sediments. Distribution of viruses closely follows distribution of bacteria, suggesting bacteria as primary hosts. The ratio of viruses to bacteria is inversely correlated to the concentration of organic C suggesting virus abundance is responsive to host substrate availability. High ratios of viruses to bacteria in mid-mat horizons (2.5 - 3.7 cm) above increasing levels of d13C in deeper horizons, coupled with a lack of increase in bacteria, suggests that viral lysis contributes to significant downward organic C (polysaccaride exudates) transport within the mat. Subsequent accumulation of d13C as well as heavier d15N in deeper sediment(denitrification)horizons elucidates tight nutrient coupling between evaporite substrate, nitrogen fixing primary producers and downcore zones of active denitrification and sulphate reduction. Discrepencies between d13C of ancient stromatolites (in line with C-3 photosynthetic pathways) and modern analogues (Badwater, CA) suggest a migration of microbial mats towards more extreme environments through time. A methodology for isotopically testing environmental and physiological responses in the geological record is presented here.

Organo-mineral complexation alters carbon and nitrogen cycling in stream microbial assemblages

NASA Astrophysics Data System (ADS)

Hunter, William Ross; Wanek, Wolfgang; Prommer, Judith; Mooshammer, Maria; Battin, Tom

2014-05-01

Inland waters are of global biogeochemical importance receiving carbon inputs of ~ 4.8 Pg C y-1. Of this 12 % is buried, 18 % transported to the oceans, and 70 % supports aquatic secondary production. However, the mechanisms that determine the fate of organic matter (OM) in these systems are poorly defined. One important aspect is the formation of organo-mineral complexes in aquatic systems and their potential as a route for OM transport and burial vs. microbial utilization as organic carbon (C) and nitrogen (N) sources. Organo-mineral particles form by sorption of dissolved OM to freshly eroded mineral surfaces and may contribute to ecosystem-scale particulate OM fluxes. We tested the availability of mineral-sorbed OM as a C & N source for streamwater microbial assemblages and streambed biofilms. Organo-mineral particles were constructed in vitro by sorption of 13C:15N-labelled amino acids to hydrated kaolin particles, and microbial degradation of these particles compared with equivalent doses of 13C:15N-labelled free amino acids. Experiments were conducted in 120 ml mesocosms over 7 days using biofilms and streamwater sampled from the Oberer Seebach stream (Austria), tracing assimilation and mineralization of 13C and 15N labels from mineral-sorbed and dissolved amino acids. Here we present data on the effects of organo-mineral sorption upon amino acid mineralization and its C:N stoichiometry. Organo-mineral sorption had a significant effect upon microbial activity, restricting C and N mineralization by both the biofilm and streamwater treatments. Distinct differences in community response were observed, with both dissolved and mineral-stabilized amino acids playing an enhanced role in the metabolism of the streamwater microbial community. Mineral-sorption of amino acids differentially affected C & N mineralization and reduced the C:N ratio of the dissolved amino acid pool. The present study demonstrates that organo-mineral complexes restrict microbial degradation of OM and may, consequently, alter the carbon and nitrogen cycling dynamics within aquatic ecosystems.

Differentiated stable isotopes signatures between pre- and post-flexion larvae of Atlantic bluefin tuna (Thunnus thynnus) and of its associated tuna species of the Balearic Sea (NW Mediterranean)

NASA Astrophysics Data System (ADS)

García, Alberto; Laiz-Carrión, Raúl; Uriarte, Amaya; Quintanilla, José M.; Morote, Elvira; Rodríguez, José M.; Alemany, Francisco

2017-06-01

The trophic ecology of bluefin tuna larvae (Thunnus thynnus) from the Balearic Sea, together with its co-existing tuna species such as albacore (T. alalunga), bullet (Auxis rochei) and little tunny (Euthynnus alletteratus) were examined by nitrogen and carbon stable isotope analyses. A total of 286 larvae were analyzed for this study, of which 72 larvae corresponded to bluefin, 57 to albacore, 81 to bullet tuna and 76 to little tunny. Tuna larvae were separated into the pre-flexion and post-flexion developmental stages. Within the size 3-9 mm standard length (SL), the stable isotope of nitrogen (δ15N) showed significant differences between species where bluefin tuna larvae ranked highest. Pre-flexion bluefin tuna and little tunny larvae showed significantly higher δ15N signatures than the post-flexion larvae. This effect is attributed to a biochemical trace of maternal δ15N signatures. However, neither albacore nor bullet tuna larvae showed this pattern in δ15N signatures, possibly owing to a compensation effect between lower maternal δ15N values transmitted to pre-flexion larvae and the early increase of δ15N values in post-flexion stages. One way ANOVA showed significant differences between species in the stable isotope ratio of carbon (δ13C) values, which suggests specific differences of carbon sources. Furthermore, a similar significant ontogenic effect between δ13C signatures of pre-flexion and post-flexion larvae is also evidenced in all four species. At pre-flexion stages, all species except bullet tuna larvae showed significant negative relationships between δ15N and larval standard length. At post-flexion stages, a significant linear relationship with larval size was only observed in albacore and bullet tuna larvae indicating a possible trophic shift towards early piscivory. With respect to δ13C values with larval size, all four species showed significant linear decreases. It may be explained by the metabolism of growth of somatic mass subject to modification of the relative carbon isotopic sources. In conclusion, the species' signatures of δ15N and δ13C indicate differentiated early life trophic niches. In addition, it is worth remarking the potential use of transgenerational isotopic transmission in future research applications.

Stable Isotope Analyses of Ancient Penguin Tissues Support the Krill Surplus Hypothesis in Antarctica

NASA Astrophysics Data System (ADS)

Emslie, S. D.; Polito, M. J.; Patterson, W. P.

2010-12-01

The krill surplus hypothesis in Antarctica is based on the premise that historic depletion of krill-eating whales and seals in the 18-20th centuries provided a surplus of krill in the southern ocean that benefited penguins. Previous study of δ13C and δ15N stable isotopes in ancient and modern tissues of Adélie Penguin (Pygoscelis adeliae) from dozens of active and abandoned colonies in Antarctica have provided the first test in support of this hypothesis (Emslie and Patterson 2007). Specifically, there is a significant decrease in both δ13C and δ15N isotope values in modern versus ancient Adélie Penguin tissues from an apparent dietary shift from fish to krill associated with the timing of the purported krill surplus. Here, we present new data on similar analyses of Gentoo Penguin (P. papua) tissues from active and abandoned colonies at two locations in the Antarctic Peninsula to determine if this species recorded a similar shift in its diet in association with the krill surplus. Our results demonstrate a significant decrease (1.5-2.0 ‰) in δ13C in modern versus fossil eggshells (two-tailed t-test of modern versus fossil mean values, t = 1.98, p < 0.0001) in accordance with this hypothesis. δ15N values are more variable among modern localities and probably were so in the past as well. Although we found a weak but significant decrease in δ15N (0.3 ‰) in modern versus fossil eggshell values, we do not consider this to be an adequate signal for a dietary shift. Our data also indicate that the decrease in δ13C values in Gentoo Penguins is not as large as that previously observed in Adélie Penguins (a 4-6 ‰ decrease in δ13C values). This weaker signal for the dietary shift in Gentoo Penguins probably results from a greater and more consistent reliance on fish, past and present, in this species compared to the Adélie Penguin. Emslie, S. D. and W. P. Patterson. 2007. Abrupt recent shift in δ13C and δ15N values in Adélie Penguin eggshell in Antarctica. Proceedings of the National Academy of Sciences 104: 11666-11669. A pair of Adélie Penguins with their well-fed chick.

Carbon and Nitrogen Isotopic Survey of Northern Peruvian Plants: Baselines for Paleodietary and Paleoecological Studies

PubMed Central

Szpak, Paul; White, Christine D.; Longstaffe, Fred J.; Millaire, Jean-François; Vásquez Sánchez, Víctor F.

2013-01-01

The development of isotopic baselines for comparison with paleodietary data is crucial, but often overlooked. We review the factors affecting the carbon (δ13C) and nitrogen (δ15N) isotopic compositions of plants, with a special focus on the carbon and nitrogen isotopic compositions of twelve different species of cultivated plants (n = 91) and 139 wild plant species collected in northern Peru. The cultivated plants were collected from nineteen local markets. The mean δ13C value for maize (grain) was −11.8±0.4 ‰ (n = 27). Leguminous cultigens (beans, Andean lupin) were characterized by significantly lower δ15N values and significantly higher %N than non-leguminous cultigens. Wild plants from thirteen sites were collected in the Moche River Valley area between sea level and ∼4,000 meters above sea level (masl). These sites were associated with mean annual precipitation ranging from 0 to 710 mm. Plants growing at low altitude sites receiving low amounts of precipitation were characterized by higher δ15N values than plants growing at higher altitudes and receiving higher amounts of precipitation, although this trend dissipated when altitude was >2,000 masl and MAP was >400 mm. For C3 plants, foliar δ13C was positively correlated with altitude and precipitation. This suggests that the influence of altitude may overshadow the influence of water availability on foliar δ13C values at this scale. PMID:23341996

Food web structure of deep-sea macrozooplankton and micronekton off the Catalan slope: Insight from stable isotopes

NASA Astrophysics Data System (ADS)

Fanelli, E.; Cartes, J. E.; Papiol, V.

2011-07-01

Food web structure of the macroplankton/micronekton fauna on the continental slope of the Catalan Sea (Balearic basin, NW Mediterranean) was investigated using carbon and nitrogen stable isotope tracers on a total of 34 taxa. Samples were collected close to Barcelona, Spain, on the middle slope, at a seasonal scale. Mean δ 13C values ranged from - 22.1‰ ( Salpa maxima) to - 16.9‰ (the mysid Eucopia hanseni). Values of δ 15N ranged from 2.5‰ (the hyperiid Vibilia armata) to 9.8‰ (the pelagic polychaete Tomopteris sp.). The stable isotope ratios of this fauna displayed a continuum of values over the δ 15N range of 7‰, confirming a wide spectrum of feeding strategies (from filter feeders to predators). High annual mean δ 15N values were found among carnivorous large zooplankton and micronekton, including species that prey on gelatinous plankton (i.e. salps, siphonophores), euphausiids, natantian decapod crustaceans and fish (i.e. myctophids and stomiiformes). In agreement with the available information on diets of planktonic taxa, the lowest isotope ratios were found for filter feeders ( V. armata, S. maxima, the pteropods Cymbulia peroni and Cavolinia inflexa, ostracods and the thaliacean Pyrosoma atlanticum), all of which feed on particulate organic matter. We found three trophic levels in macroplankton/micronekton food webs based on a 15N-enrichment factor of ~ 2.5‰ per level. The range of δ 13C was particularly wide among carnivores (- 20.7‰ to - 16.6‰), suggesting predation on a variety of prey from gelatinous zooplankton (which displayed more depleted δ 13C signatures) to small fishes and decapods. Correlation between δ 13C-δ 15N was generally weak, likely due to the consumption of different kinds of sinking particles (e.g. marine snow, phytodetritus), some constituted of multiply recycled particulate organic matter (POM). However, higher δ 13C-δ 15N correlations were observed during winter and spring, periods of water column homogenization, suggesting that the planktonic community assimilates pulses of new production from the photic zone (peaking in January-February). Low correlations were observed during periods of water column stratification, particularly in summer, when production is especially low, suggesting that in this period macroplankton-micronekton community rely on sources other than surface primary production such as POM derived from river discharge.

Solution structure of the DNA-binding domain of the heat shock transcription factor determined by multidimensional heteronuclear magnetic resonance spectroscopy.

PubMed Central

Damberger, F. F.; Pelton, J. G.; Harrison, C. J.; Nelson, H. C.; Wemmer, D. E.

1994-01-01

The solution structure of the 92-residue DNA-binding domain of the heat shock transcription factor from Kluyveromyces lactis has been determined using multidimensional NMR methods. Three-dimensional (3D) triple resonance, 1H-13C-13C-1H total correlation spectroscopy, and 15N-separated total correlation spectroscopy-heteronuclear multiple quantum correlation experiments were used along with various 2D spectra to make nearly complete assignments for the backbone and side-chain 1H, 15N, and 13C resonances. Five-hundred eighty-three NOE constraints identified in 3D 13C- and 15N-separated NOE spectroscopy (NOESY)-heteronuclear multiple quantum correlation spectra and a 4-dimensional 13C/13C-edited NOESY spectrum, along with 35 phi, 9 chi 1, and 30 hydrogen bond constraints, were used to calculate 30 structures by hybrid distance geometry/stimulated annealing protocol, of which 24 were used for structural comparison. The calculations revealed that a 3-helix bundle packs against a small 4-stranded antiparallel beta-sheet. The backbone RMS deviation (RMSD) for the family of structures was 1.03 +/- 0.19 A with respect to the average structure. The topology is analogous to that of the C-terminal domain of the catabolite gene activator protein and appears to be in the helix-turn-helix family of DNA-binding proteins. The overall fold determined by the NMR data is consistent with recent crystallographic work on this domain (Harrison CJ, Bohm AA, Nelson HCM, 1994, Science 263:224) as evidenced by RMSD between backbone atoms in the NMR and X-ray structures of 1.77 +/- 0.20 A. Several differences were identified some of which may be due to protein-protein interactions in the crystal. PMID:7849597

Effects of euthanasia methods on stable carbon (δ13 C value) and nitrogen (δ15 N value) isotopic compositions of fry and juvenile rainbow trout Oncorhynchus mykiss.

PubMed

Nahon, Sarah; Séité, Sarah; Kolasinski, Joanna; Aguirre, Pierre; Geurden, Inge

2017-10-30

Carbon and nitrogen stable isotope analyses of fish tissues are now commonly used in ecological studies but mostly require the sacrifice of the animal. Ethical considerations recommend the use of anesthetics for tissue sampling. This study examines how anesthetics affect stable isotope ratios of fish compared with other euthanasia methods. Rainbow trout fry and juveniles were sacrificed using ice-freezing (as this common method used to kill fish does not affect natural isotopic ratios), electronarcosis or an overdose of chemical anesthetics (2-phenoxyethanol, benzocaine and clove oil). For fry, we sampled the whole animal whereas, for juveniles, white dorsal muscle, liver, red blood cells, plasma, external tegument and pectoral fin were sampled. Isotopic ratios and the elemental compositions of carbon and nitrogen were then measured. The δ 15 N values, and the C and N contents of all considered tissues as well as δ 13 C values of muscle, liver, red blood cells and plasma, were not affected by the use of chemical anesthetics. Clove oil and to a lesser extent 2-phenoxyethanol and benzocaine decreased δ 13 C values of whole fry and juvenile external tegument and pectoral fin. The use of electronarcosis drastically affects the δ 13 C and δ 15 N values of all fish tissues. Anesthetics should be avoided for δ 13 C analysis when tissues are in contact with the water containing the anesthetic. Ice-immersion has to be preferred when approved by guidelines. If not, benzocaine and 2-phenoxyethanol should be preferred over clove oil. Electronarcosis should not be used to kill fish until further investigations are performed. Copyright © 2017 John Wiley & Sons, Ltd.

Allocation of Nitrogen and Carbon Is Regulated by Nodulation and Mycorrhizal Networks in Soybean/Maize Intercropping System

PubMed Central

Wang, Guihua; Sheng, Lichao; Zhao, Dan; Sheng, Jiandong; Wang, Xiurong; Liao, Hong

2016-01-01

Soybean/maize intercropping has remarkable advantages in increasing crop yield and nitrogen (N) efficiency. However, little is known about the contributions of rhizobia or arbuscular mycorrhizal fungi (AMF) to yield increases and N acquisition in the intercropping system. Plus, the mechanisms controlling carbon (C) and N allocation in intercropping systems remain unsettled. In the present study, a greenhouse experiment combined with 15N and 13C labeling was conducted using various inoculation and nutrient treatments. The results showed that co-inoculation with AMF and rhizobia dramatically increased biomass and N content of soybean and maize, and moderate application of N and phosphorus largely amplified the effect of co-inoculation. Maize had a competitive advantage over soybean only under co-inoculation and moderate nutrient availability conditions, indicating that the effects of AMF and rhizobia in intercropping systems are closely related to nutrient status. Results from 15N labeling showed that the amount of N transferred from soybean to maize in co-inoculations was 54% higher than that with AMF inoculation alone, with this increased N transfer partly resulting from symbiotic N fixation. The results from 13C labeling showed that 13C content increased in maize shoots and decreased in soybean roots with AMF inoculation compared to uninoculated controls. Yet, with co-inoculation, 13C content increased in soybean. These results indicate that photosynthate assimilation is stimulated by AM symbiosis in maize and rhizobial symbiosis in soybean, but AMF inoculation leads to soybean investing more carbon than maize into common mycorrhizal networks (CMNs). Overall, the results herein demonstrate that the growth advantage of maize when intercropped with soybean is due to acquisition of N by maize via CMNs while this crop contributes less C into CMNs than soybean under co-inoculation conditions. PMID:28018420

Allocation of Nitrogen and Carbon Is Regulated by Nodulation and Mycorrhizal Networks in Soybean/Maize Intercropping System.

PubMed

Wang, Guihua; Sheng, Lichao; Zhao, Dan; Sheng, Jiandong; Wang, Xiurong; Liao, Hong

2016-01-01

Soybean/maize intercropping has remarkable advantages in increasing crop yield and nitrogen (N) efficiency. However, little is known about the contributions of rhizobia or arbuscular mycorrhizal fungi (AMF) to yield increases and N acquisition in the intercropping system. Plus, the mechanisms controlling carbon (C) and N allocation in intercropping systems remain unsettled. In the present study, a greenhouse experiment combined with 15 N and 13 C labeling was conducted using various inoculation and nutrient treatments. The results showed that co-inoculation with AMF and rhizobia dramatically increased biomass and N content of soybean and maize, and moderate application of N and phosphorus largely amplified the effect of co-inoculation. Maize had a competitive advantage over soybean only under co-inoculation and moderate nutrient availability conditions, indicating that the effects of AMF and rhizobia in intercropping systems are closely related to nutrient status. Results from 15 N labeling showed that the amount of N transferred from soybean to maize in co-inoculations was 54% higher than that with AMF inoculation alone, with this increased N transfer partly resulting from symbiotic N fixation. The results from 13 C labeling showed that 13 C content increased in maize shoots and decreased in soybean roots with AMF inoculation compared to uninoculated controls. Yet, with co-inoculation, 13 C content increased in soybean. These results indicate that photosynthate assimilation is stimulated by AM symbiosis in maize and rhizobial symbiosis in soybean, but AMF inoculation leads to soybean investing more carbon than maize into common mycorrhizal networks (CMNs). Overall, the results herein demonstrate that the growth advantage of maize when intercropped with soybean is due to acquisition of N by maize via CMNs while this crop contributes less C into CMNs than soybean under co-inoculation conditions.

1H, 13C, 15N NMR analysis of sildenafil base and citrate (Viagra) in solution, solid state and pharmaceutical dosage forms.

PubMed

Wawer, Iwona; Pisklak, Maciej; Chilmonczyk, Zdzisław

2005-08-10

Sildenafil citrate (SC) (Viagra) and sildenafil base in pure form are easily and unequivocally characterized by multinuclear NMR spectroscopy. Analysis of chemical shifts indicates that: (i) N6-H forms intramolecular hydrogen bonds, (ii) N25 is protonated in the salt and (iii) intermolecular OH...N hydrogen bonds involving N2 and N4 are present in the solid sildenafil citrate. 13C CPMAS NMR method has been proposed for the identification and quantitation of Viagra in its pharmaceutical formulations.

Applicability of stable C and N isotope analysis in inferring the geographical origin and authentication of commercial fish (Mackerel, Yellow Croaker and Pollock).

PubMed

Kim, Heejoong; Suresh Kumar, K; Shin, Kyung-Hoon

2015-04-01

Globalisation of seafood and aquaculture products and their convenient marketing worldwide, increases the possibility for the distribution of mislabelled products; thereby, underlining the need to identify their origin. Stable isotope analysis is a promising approach to identify the authenticity and traceability of seafood and aquaculture products. In this investigation, we measured carbon and nitrogen stable isotope ratios (δ(13)C and δ(15)N) of three commercial fish, viz. Mackerel, Yellow Croaker and Pollock, originating from various countries. Apart from the species-dependent variation in the isotopic values, marked differences in the δ(13)C and δ(15)N ratios were also observed with respect to the country of origin. This suggests that C and N isotopic signatures could be reliable tools to identify and trace the origin of commercial fish. Copyright © 2014 Elsevier Ltd. All rights reserved.

Benthic macroinvertebrate and fish communities in Lake Huron are linked to submerged groundwater vents

USGS Publications Warehouse

Garrison, Sanders T.; Biddanda, B.A.; Stricker, C.A.; Nold, S.C.

2011-01-01

Groundwater can be an important source of nutrients and energy to aquatic ecosystems, but quantifying the inputs and biogeochemical importance remains challenging. A series of submerged groundwater vents in northern Lake Huron were examined to determine the linkage between groundwater nutrients and aquatic food webs. We collected samples of key food-web components from groundwater vent and reference habitats and analyzed them for 13C, 15N, and 34S isotopes. Dissolved inorganic carbon (DIC) in the groundwater was depleted in 13C, while aqueous sulfate was enriched in 34S (mean differences between groundwater and reference sites were -3.9% and +12.0%, respectively). Benthic primary producers, macroinvertebrates, and benthivorous fish had significantly lower ??13C values in groundwater environments, and benthivorous fish were somewhat depleted (-2.5%) in ??34S at groundwater sites compared to reference sites. However, ??15N values were not different between groundwater and reference sites, and pelagic components of the ecosystems (plankton and planktivorous and piscivorous fish) were similar in both ??13C and ??15N. These data suggest benthic metazoan communities surrounding groundwater vents are partially linked to groundwater-derived benthic primary production, while planktivorous and piscivorous communities not directly associated with the benthos do not rely on groundwater nutrients. ?? Inter-Research 2011.

Vertical movement of adult rusty grain beetles, Cryptolestes ferrugineus, in stored corn and wheat at uniform moisture content

PubMed Central

Jian, Fuji; Jayas, Digvir S.; White, Noel D. G.

2006-01-01

Vertical movement and distribution of Cryptolestes ferrugineus (Coleoptera: Laemophloeidae) adults in stored wheat and corn were studied in small (0.1 x 0.1 x 1 m) and large (0.6 m diameter and 1.12 m high) columns. The adults were introduced at the top, middle, and bottom of the small columns with a uniform moisture content (wheat: 14.5 ± 0.1%, corn 13.5 ± 0.1%, 15.5 ± 0.1%, and 17.5 ± 0.1%) at 27.5 ± 0.5°C. When introduced at different locations, adults showed a similar distribution in stored grain bulk with a uniform temperature and moisture content of 14.5% for wheat or 15.5% for corn. Adults showed downward displacement over 24 h when corn moisture was lower than 15.5%, but they did not show downward displacement when moisture content was 17.5%. The upward or downward movement might partially be caused by a drift effect due to beetles sliding between seeds and the displacement of the adults might be the combined effect of walking and falling during their movement. The hydrophilic behavior plus the drift effect explain why the beetles had a faster downward dispersal in the 13.5% corn than in the 15.5% and 17.5% corn and a slight upward displacement in 17.5% corn because they were more active at the lower moisture contents. Adults had a similar movement and distribution in both the small and large wheat columns. PMID:19537976

Gyroscope-like molecules consisting of PdX₂/PtX₂ rotators within three-spoke dibridgehead diphosphine stators: syntheses, substitution reactions, structures, and dynamic properties.

PubMed

Nawara-Hultzsch, Agnieszka J; Stollenz, Michael; Barbasiewicz, Michał; Szafert, Sławomir; Lis, Tadeusz; Hampel, Frank; Bhuvanesh, Nattamai; Gladysz, John A

2014-04-14

Threefold intramolecular ring-closing metatheses of trans-[MCl2(P{(CH2)(m)CH=CH2}3)2] are effected with Grubbs' catalyst. Following hydrogenation catalyzed by [RhCl(PPh3)3], the title complexes trans-[MCl2(P((CH2)n)3P)] (n=2m+2; M/n=Pt/14, 4 c; Pt/16, 4 d; Pt/18, 4 e; Pd/14, 5 c; Pd/18, 5 e) and sometimes isomers partly derived from intraligand metathesis, trans-[MCl2{P(CH2)n(CH2)n}P(CH2)n)] (4'c-e, 5'e), are isolated. These react with LiBr, NaI, and KCN to give the corresponding MBr2, MI2, and M(CN)2 species (58-99%). (13)C NMR data show that the MX2 moieties rapidly rotate within the diphosphine cage on the NMR timescale, even at -120 °C. The reaction of 4 c and KSCN gives separable Pt(NCS)2 and Pt(NCS)(SCN) adducts (13 c, 28%; 14 c, 20%), and those of 4 c,e and Ph2Zn give PtPh2 species (15 c, 61%; 15 e, 90%). (13)C NMR spectra of 13 c-15 c show two sets of CH2 signals (ca. 2:1 intensity ratios), indicating that MX2 rotation is no longer rapid. Reactions of 4 c or 4'c and excess NaC≡CH afford the free diphosphines P{(CH2)14}3P (91%) and (CH2)14P(CH2)14P(CH2)14 (90%). The latter has been crystallographically characterized as a bis(BH3) adduct. The crystal structures of eight complexes with P(CH2)14P linkages (PtCl2, PtBr2, PtI2, Pt(NCS)2, PtPh2, PdCl2, PdBr2, PdI2) and 15 e have been determined, and intramolecular distances analyzed with respect to MX2 rotation. The conformations of the (CH2)14 moieties and features of the crystal lattices are also discussed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

NASA Astrophysics Data System (ADS)

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

2016-02-01

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

15 CFR 14.13 - Debarment and suspension.

Code of Federal Regulations, 2010 CFR

2010-01-01

... 15 Commerce and Foreign Trade 1 2010-01-01 2010-01-01 false Debarment and suspension. 14.13 Section 14.13 Commerce and Foreign Trade Office of the Secretary of Commerce UNIFORM ADMINISTRATIVE... shall comply with the nonprocurement debarment and suspension common rule implementing E.O.s 12549 and...

15 CFR 14.13 - Debarment and suspension.

Code of Federal Regulations, 2011 CFR

2011-01-01

... 15 Commerce and Foreign Trade 1 2011-01-01 2011-01-01 false Debarment and suspension. 14.13 Section 14.13 Commerce and Foreign Trade Office of the Secretary of Commerce UNIFORM ADMINISTRATIVE... shall comply with the nonprocurement debarment and suspension common rule implementing E.O.s 12549 and...

15 CFR 14.13 - Debarment and suspension.

Code of Federal Regulations, 2014 CFR

2014-01-01

... 15 Commerce and Foreign Trade 1 2014-01-01 2014-01-01 false Debarment and suspension. 14.13 Section 14.13 Commerce and Foreign Trade Office of the Secretary of Commerce UNIFORM ADMINISTRATIVE... shall comply with the nonprocurement debarment and suspension common rule implementing E.O.s 12549 and...

15 CFR 14.13 - Debarment and suspension.

Code of Federal Regulations, 2013 CFR

2013-01-01

... 15 Commerce and Foreign Trade 1 2013-01-01 2013-01-01 false Debarment and suspension. 14.13 Section 14.13 Commerce and Foreign Trade Office of the Secretary of Commerce UNIFORM ADMINISTRATIVE... shall comply with the nonprocurement debarment and suspension common rule implementing E.O.s 12549 and...

Probing intermolecular interactions in a diethylcarbamazine citrate salt by fast MAS 1H solid-state NMR spectroscopy and GIPAW calculations.

PubMed

Venâncio, Tiago; Oliveira, Lyege Magalhaes; Ellena, Javier; Boechat, Nubia; Brown, Steven P

2017-10-01

Fast magic-angle spinning (MAS) NMR is used to probe intermolecular interactions in a diethylcarbamazine salt, that is widely used as a treatment against adult worms of Wuchereria bancrofti which cause a common disease in tropical countries named filariasis. Specifically, a dihydrogen citrate salt that has improved thermal stability and solubility as compared to the free form is studied. One-dimensional 1 H, 13 C and 15 N and two-dimensional 1 H- 13 C and 14 N- 1 H heteronuclear correlation NMR experiments under moderate and fast MAS together with GIPAW (CASTEP) calculations enable the assignment of the 1 H, 13 C and 14 N/ 15 N resonances. A two-dimensional 1 H- 1 H double-quantum (DQ) -single-quantum (SQ) MAS spectrum recorded with BaBa recoupling at 60kHz MAS identifies specific proton-proton proximities associated with citrate-citrate and citrate-diethylcarbamazine intermolecular interactions. Copyright © 2017 Elsevier Inc. All rights reserved.

Growth rate and stable carbon and nitrogen isotope trophic discrimination factors of lion and leopard whiskers.

PubMed

Mutirwara, Ruwimbo; Radloff, Frans G T; Codron, Daryl

2018-01-15

Stable isotope analysis (SIA) of whiskers has been used to identify temporal feeding habits, intra-population diet variation, as well as individual dietary specialisation of marine and terrestrial carnivores. However, the potential of the method to disclose such dietary information for large wild felids is hampered by lack of information on species-specific whisker growth rates, whisker growth patterns and whisker-diet trophic discrimination factors (TDFs). Whisker growth rates and growth patterns were measured for four lions (Panthera leo) and one leopard (Panthera pardus) held at the National Zoological Gardens, Pretoria, South Africa. Actively growing whiskers of the felids were 'marked' four times over 185 days using 13 C-depleted, C 3 -based giraffe (Giraffa camelopardalis) meat. The periods with low δ 13 C values, identified following serial sectioning of the regrown whiskers at 1 mm intervals and isotopic analysis, were then correlated to specific giraffe meat feeding bouts and hence growth periods. δ 13 C and δ 15 N whisker-diet TDFs were estimated for five lions whose diet remained consistent over multiple years. The whisker growth rates of three lionesses and the leopard were similar (mean = 0.65 mm day -1 ), despite species, sex and age differences. There was a decrease in whisker growth rate over time, suggesting a non-linear whisker growth pattern. However, linear and non-linear growth simulations showed slight differences between the two growth patterns for the proximal ~50 mm of whiskers. δ 13 C and δ 15 N lion whisker-diet TDFs were also similar amongst individuals (mean = 2.7 ± 0.12 ‰ for δ 13 C values and 2.5 ± 0.08 ‰ for δ 15 N values), irrespective of age and sex. The whisker growth rate and δ 13 C and δ 15 N lion whisker-diet TDFs obtained in this study can be applied in future studies to assign dietary information contained in analysed felid whiskers to the correct time period and improve deductions of prey species consumed by wild felids. Copyright © 2017 John Wiley & Sons, Ltd.

The Coast Artillery Journal. Volume 74, Number 3, March-April 1931

DTIC Science & Technology

1931-04-01

beC’n destl’oye,1. 1st Sgt, Fern, Capt. Bowering, Lieut. McGuire The Cost of the National Guard Colonel William H. Waldron, Executive Officer, Militia...Mont 16% 41. Tenn 15% 42. Ya 15% 43. La 14% 44. Mo 14% 45. N. M 14% 46. Ala 13% 47. Miss 13% 48. Idaho 11% 49. s. D. "’"’’’’ .. 11% 50. :Nev 9% 51...Delaware n .n ._n __ i58 District of Columbia ._n 922 Florida ._nn n __n .n __.. 2,269 ~~~;:f.============================= 1:~~~ Idaho . .. .n nnn 1,163

Variation in stable isotopes of freshwater mussel shells in a Kentucky river system

NASA Astrophysics Data System (ADS)

Erhardt, A. M.; Haag, W.; Price, S.; Weisrock, D.

2017-12-01

Isotopic signatures in freshwater mussel shells can reflect environmental differences among streams and human impacts on river systems. In the southeastern United States, mussels exhibit extraordinary biodiversity, serve an important role as filter feeders, and are sensitive to environmental change. Additionally, their long life-span (up to 50 years) and seasonal shell deposition can permit high-resolution environmental reconstructions. We examined variation in shell stable isotope values among mussel species and locations throughout the Licking River system in Kentucky. We sampled 8 species at 11 locations. These species represented a range of life-history traits, and locations were distributed among tributaries and the main stem of the Licking River. Samples of the outer organic periostracum layer were analysed for organic δ13C and δ15N, while organic δ15N and inorganic δ13C and δ18O were measured in the inner carbonate portion of the shell. At the same location, preliminary results show variations 2‰ in δ13C and 1‰ in δ15N between different species. We suspect these relationships are due to variations in diet and/or body size. Some, though not all, specimens show variation along the growth axis. For the same species at different locations, preliminary results showed a range of 4‰ in δ13C and 10‰ in δ15N values. Isotope ratios of specimens from the main stem were distinct from those of specimens from the river's largest tributary. Overall, δ13C shows distinct values for each tributary, while δ15N shows a general decline downstream. These variations are likely the result of environmental factors such as the degree of karstification and the ratio of forest to pasture within the catchment. We hope to use this study to identify if any isotopically distinct sources, such as fertilizers or animal manure, contribute to the high nutrient load in these systems. These results represent an exploratory effort to describe watershed-scale and mussel community patterns of isotope variation, allowing us to attempt to unravel the anthropogenic influence on this highly biodiverse and environmentally sensitive organism.

Changing gull diet in a changing world: a 150-year stable isotope (δ13C, 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 population declines in this species and other piscivores. © 2014 John Wiley & Sons Ltd.

Stable isotopes, beaks and predators: a new tool to study the trophic ecology of cephalopods, including giant and colossal squids.

PubMed

Cherel, Yves; Hobson, Keith A

2005-08-07

Cephalopods play a key role in the marine environment but knowledge of their feeding habits is limited by lack of data. Here, we have developed a new tool to investigate their feeding ecology by combining the use of their predators as biological samplers together with measurements of the stable isotopic signature of their beaks. Cephalopod beaks are chitinous hard structures that resist digestion and the stable isotope ratios of carbon (delta13C) and nitrogen (delta15N) are indicators of the foraging areas and trophic levels of consumers, respectively. First, a comparison of delta13C and delta15N values of different tissues from the same individuals showed that beaks were slightly enriched in 13C but highly impoverished in 15N compared with lipid-free muscle tissues. Second, beaks from the same species showed a progressive increase in their delta15N values with increasing size, which is in agreement with a dietary shift from lower to higher trophic levels during cephalopod growth. In the same way, there was an increase in the delta15N signature of various parts of the same lower beaks in the order rostrum, lateral walls and wings, which reflects the progressive growth and chitinization of the beaks in parallel with dietary changes. Third, we investigated the trophic structure of a cephalopod community for the first time. Values of delta15N indicate that cephalopods living in slope waters of the subantarctic Kerguelen Islands (n=18 species) encompass almost three distinct trophic levels, with a continuum of two levels between crustacean- and fish-eaters and a distinct higher trophic level occupied by the colossal squid Mesonychoteuthis hamiltoni. delta13C values demonstrated that cephalopods grow in three different marine ecosystems, with 16 species living and developing in Kerguelen waters and two species migrating from either Antarctica (Slosarczykovia circumantarctica) or the subtropics (the giant squid Architeuthis dux). The stable isotopic signature of beaks accumulated in predators' stomachs therefore revealed new trophic relationships and migration patterns and is a powerful tool to investigate the role of the poorly known cephalopods in the marine environment.

Isotope (δ13C, δ15N, δ2H) diet-tissue discrimination in African grey parrot Psittacus erithacus: implications for forensic studies.

PubMed

Symes, Craig; Skhosana, Felix; Butler, Mike; Gardner, Brett; Woodborne, Stephan

2017-12-01

Diet-tissue isotopic relationships established under controlled conditions are informative for determining the dietary sources and geographic provenance of organisms. We analysed δ 13 C, δ 15 N, and non-exchangeable δ 2 H values of captive African grey parrot Psittacus erithacus feathers grown on a fixed mixed-diet and borehole water. Diet-feather Δ 13 C and Δ 15 N discrimination values were +3.8 ± 0.3 ‰ and +6.3 ± 0.7 ‰ respectively; significantly greater than expected. Non-exchangeable δ 2 H feather values (-62.4 ± 6.4 ‰) were more negative than water (-26.1 ± 2.5 ‰) offered during feather growth. There was no positive relationship between the δ 13 C and δ 15 N values of the samples along each feather with the associated samples of food offered, or the feather non-exchangeable hydrogen isotope values with δ 2 H values of water, emphasising the complex processes involved in carbohydrate, protein, and income water routing to feather growth. Understanding the isotopic relationship between diet and feathers may provide greater clarity in the use of stable isotopes in feathers as a tool in determining origins of captive and wild-caught African grey parrots, a species that is widespread in aviculture and faces significant threats to wild populations. We suggest that these isotopic results, determined even in controlled laboratory conditions, be used with caution.

Stable carbon and nitrogen isotope values of dorsal spine age rings indicate temporal variation in the diet of striped marlin (Kajikia audax) in waters around Cabo San Lucas, Mexico.

PubMed

Acosta-Pachón, Tatiana A; Ortega-García, Sofia; Graham, Brittany

2015-09-30

Billfishes, such as marlin, are top pelagic predators that play an important role in maintaining the stability of marine food webs. Notwithstanding the importance of these species, there remain gaps in our knowledge on their movements, foraging, and trophic status in the early stage of life. We measured the δ(13)C and δ(15)N values in each annual growth band deposited in the dorsal spine from striped marlin caught off Cabo San Lucas, Mexico, to produce retrospective isotopic profiles that would enable us to detect any significant isotopic changes across development. The samples were analyzed using an elemental analyzer coupled to an isotope ratio mass spectrometer. There was no relationship between the size of striped marlin and the δ(15) N values. Differences in δ(15)N mean values across different age classes were not significant and the variation in δ(15)N values through the marlins' life cycle was less than 2‰. However, the mean δ(15)N values between individuals varied by up to 6‰. The δ(13)C values increased as a function of age, and the mean δ(13)C values varied significantly between age classes. Fin spines can be used to construct retrospective isotopic histories for the investigation of trophic dynamics and migratory histories in billfishes, for which population dynamics are often poorly known. Copyright © 2015 John Wiley & Sons, Ltd.

Biomagnification of Mercury in Fish from Two Gold Mining-Impacted Tropical Marshes in Northern Colombia.

PubMed

Marrugo-Negrete, José Luis; Ruiz-Guzmán, Javier Alonso; Ruiz-Fernández, Ana Carolina

2018-01-01

Total mercury concentrations (T-Hg) and stable isotope ratios (δ 15 N and δ 13 C) were analyzed in the muscle of fish, collected at two marshes impacted by gold mining in Northern Colombia, to evaluate the seasonal and spatial behavior of these variables and mercury biomagnification based on their relationship with δ 15 N ratios in the fish. There was not significant (p > 0.05) seasonal differences (dry and rainy season) in δ 15 N and δ 13 C values in none marsh, suggesting that these fish species keep a similar feed pattern within each marsh along the year. However, there were significant differences (p < 0.05) between marshes in δ 15 N, δ 13 C, and T-Hg, as well as significant seasonal differences (p < 0.05) in T-Hg values for some species, suggesting the possible influence of factors, such as differences in length of food chains between marshes and different degree of anthropogenic impact in relation to human settlements, farmland, livestock (higher in Ayapel marsh), and gold mining activity (higher in La Raya marsh). Correlations analysis showed significant (p < 0.05) relationships between T-Hg concentrations and δ 15 N values, as well as trophic level, evidencing a T-Hg biomagnification process in the fish food chain from both marshes and consequently a potential health risk for human riverside inhabitants who eat these fish.

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

PubMed

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

2009-11-01

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

Probing the experimental phonon dispersion of graphene using 12C and 13C isotopes

NASA Astrophysics Data System (ADS)

Bernard, S.; Whiteway, E.; Yu, V.; Austing, D. G.; Hilke, M.

2012-08-01

Using very uniform large-scale chemical vapor deposition grown graphene transferred onto silicon, we were able to identify 15 distinct Raman lines associated with graphene monolayers. This was possible thanks to a combination of different carbon isotopes and different Raman laser energies and extensive averaging without increasing the laser power. This allowed us to obtain a detailed experimental phonon dispersion relation for many points in the Brillouin zone. We further identified a D+D' peak corresponding to a double-phonon process involving both an inter- and intravalley phonon.

3D TOCSY-HSQC NMR for metabolic flux analysis using non-uniform sampling

DOE PAGES

Reardon, Patrick N.; Marean-Reardon, Carrie L.; Bukovec, Melanie A.; ...

2016-02-05

13C-Metabolic Flux Analysis ( 13C-MFA) is rapidly being recognized as the authoritative method for determining fluxes through metabolic networks. Site-specific 13C enrichment information obtained using NMR spectroscopy is a valuable input for 13C-MFA experiments. Chemical shift overlaps in the 1D or 2D NMR experiments typically used for 13C-MFA frequently hinder assignment and quantitation of site-specific 13C enrichment. Here we propose the use of a 3D TOCSY-HSQC experiment for 13C-MFA. We employ Non-Uniform Sampling (NUS) to reduce the acquisition time of the experiment to a few hours, making it practical for use in 13C-MFA experiments. Our data show that the NUSmore » experiment is linear and quantitative. Identification of metabolites in complex mixtures, such as a biomass hydrolysate, is simplified by virtue of the 13C chemical shift obtained in the experiment. In addition, the experiment reports 13C-labeling information that reveals the position specific labeling of subsets of isotopomers. As a result, the information provided by this technique will enable more accurate estimation of metabolic fluxes in larger metabolic networks.« less

Relating Carbon and Nitrogen Isotope Effects to Reaction Mechanisms during Aerobic or Anaerobic Degradation of RDX (Hexahydro-1,3,5-Trinitro-1,3,5-Triazine) by Pure Bacterial Cultures

PubMed Central

Heraty, Linnea; Condee, Charles W.; Vainberg, Simon; Sturchio, Neil C.; Böhlke, J. K.; Hatzinger, Paul B.

2016-01-01

ABSTRACT Kinetic isotopic fractionation of carbon and nitrogen during RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) biodegradation was investigated with pure bacterial cultures under aerobic and anaerobic conditions. Relatively large bulk enrichments in 15N were observed during biodegradation of RDX via anaerobic ring cleavage (ε15N = −12.7‰ ± 0.8‰) and anaerobic nitro reduction (ε15N = −9.9‰ ± 0.7‰), in comparison to smaller effects during biodegradation via aerobic denitration (ε15N = −2.4‰ ± 0.2‰). 13C enrichment was negligible during aerobic RDX biodegradation (ε13C = −0.8‰ ± 0.5‰) but larger during anaerobic degradation (ε13C = −4.0‰ ± 0.8‰), with modest variability among genera. Dual-isotope ε13C/ε15N analyses indicated that the three biodegradation pathways could be distinguished isotopically from each other and from abiotic degradation mechanisms. Compared to the initial RDX bulk δ15N value of +9‰, δ15N values of the NO2− released from RDX ranged from −7‰ to +2‰ during aerobic biodegradation and from −42‰ to −24‰ during anaerobic biodegradation. Numerical reaction models indicated that N isotope effects of NO2− production were much larger than, but systematically related to, the bulk RDX N isotope effects with different bacteria. Apparent intrinsic ε15N-NO2− values were consistent with an initial denitration pathway in the aerobic experiments and more complex processes of NO2− formation associated with anaerobic ring cleavage. These results indicate the potential for isotopic analysis of residual RDX for the differentiation of degradation pathways and indicate that further efforts to examine the isotopic composition of potential RDX degradation products (e.g., NOx) in the environment are warranted. IMPORTANCE This work provides the first systematic evaluation of the isotopic fractionation of carbon and nitrogen in the organic explosive RDX during degradation by different pathways. It also provides data on the isotopic effects observed in the nitrite produced during RDX biodegradation. Both of these results could lead to better understanding of the fate of RDX in the environment and help improve monitoring and remediation technologies. PMID:27016566

Authenticity testing of environment-friendly Korean rice (Oryza sativa L.) using carbon and nitrogen stable isotope ratio analysis.

PubMed

Chung, Ill-Min; Park, Sung-Kyu; Lee, Kyoung-Jin; An, Min-Jeong; Lee, Ji-Hee; Oh, Yong-Taek; Kim, Seung-Hyun

2017-11-01

The increasing demand for organic foods creates, in turn, a pressing need for the development of more accurate tools for the authentication of organic food in order to ensure both fair trade and food safety. This study examines the feasibility of δ 13 C and δ 15 N analyses as potential tools for authentication of environment-friendly rice sold in Korea. δ 13 C and δ 15 N examination in different rice grains showed that environment-friendly rice can be successfully distinguished from conventional rice. No multi-residue pesticides were detected in the examined rice samples, including conventional rice. This study demonstrates the complementary feasibility of δ 13 C and δ 15 N analyses for the authentication of environment-friendly rice sold in Korea in cases where pesticide residue analysis alone is insufficient for discrimination of organic and conventional rice. In future, complementary analyses including compound-specific isotope ratio analysis might be employed for improving the reliability of organic authentication. Copyright © 2017 Elsevier Ltd. All rights reserved.

Diet-tissue discrimination factors and turnover of carbon and nitrogen stable isotopes in tissues of an adult predatory coral reef fish, Plectropomus leopardus.

PubMed

Matley, J K; Fisk, A T; Tobin, A J; Heupel, M R; Simpfendorfer, C A

2016-01-15

Stable isotope ratios (δ(13)C and δ(15)N values) provide a unique perspective into the ecology of animals because the isotope ratio values of consumers reflect the values in food. Despite the value of stable isotopes in ecological studies, the lack of species-specific experimentally derived diet-tissue discrimination factors (DTDFs) and turnover rates limits their application at a broad scale. Furthermore, most aquatic feeding experiments use temperate, fast-growing fish species and few have considered medium- to large-sized adults with low growth rates from tropical ecosystems. A controlled-diet stable isotope feeding trial was conducted over a 196-day period for the adult predatory reef fish leopard coralgrouper (Plectropomus leopardus). This study calculated δ(13)C and δ(15)N DTDFs and turnover rates in five tissues (liver, plasma, red blood cells (RBC), fin, and muscle) using a continuous flow isotope ratio mass spectrometer equipped with an elemental analyzer. In addition, the effect of chemical lipid extraction (LE) on stable isotope values was examined for each tissue. Turnover was mainly influenced by metabolism (as opposed to growth) with LE δ(15)N half-life values lowest in fin (37 days) and plasma (66 days), and highest in RBC (88 days) and muscle (126 days). The diet-tissue discrimination factors for δ(15)N values in all tissues (Δ(15)N: -0.15 to 1.84‰) were typically lower than commonly reported literature values. Lipid extraction altered both δ(15) N and δ(13)C values compared with untreated samples; however, for the δ(15)N values, the differences were small (mean δ(15)N(LE-Bulk) <0.46‰ in all tissues). This study informs future interpretation of stable isotope data for medium- to large-sized fish and demonstrates that DTDFs developed for temperate fish species, particularly for δ(15)N values, may not apply to tropical species. Sampling of muscle and/or RBC is recommended for a relatively long-term representation of feeding habits, while plasma and/or fin should be used for a more recent indication of diet. Copyright © 2015 John Wiley & Sons, Ltd.

The nature of organic carbon in density-fractionated sediments in the Sacramento-San Joaquin River Delta (California)

NASA Astrophysics Data System (ADS)

Wakeham, S. G.; Canuel, E. A.

2015-10-01

Rivers are the primary means by which sediments and carbon are transported from the terrestrial biosphere to the oceans but gaps remain in our understanding of carbon associations from source to sink. Bed sediments from the Sacramento-San Joaquin River Delta (CA) were fractionated according to density and analyzed for sediment mass distribution, elemental (C and N) composition, mineral surface area, and stable carbon and radiocarbon isotope compositions of organic carbon (OC) and fatty acids to evaluate the nature of organic carbon in river sediments. OC was unevenly distributed among density fractions. Mass and TOC were in general concentrated in mesodensity (1.6-2.0 and 2.0-2.5 g cm-3) fractions, comprising 84.0 ± 1.3 % of total sediment mass and 80.8 ± 13.3 % of total OC (TOC). Low density (< 1.6 g cm-3) material, although rich in OC (34.0 ± 2.0 % OC) due to woody debris, constituted only 17.3 ± 12.8 % of TOC. High density (> 2.5 g cm-3) organic-poor, mineral material made-up 13.7 ± 1.4 % of sediment mass and 2.0 ± 0.9 % of TOC. Stable carbon isotope compositions of sedimentary OC were relatively uniform across bulk and density fractions (δ13C -27.4 ± 0.5 ‰). Radiocarbon content varied from Δ14C values of -382 (radiocarbon age 3800 yr BP) to +94 ‰ (modern) indicating a~mix of young and pre-aged OC. Fatty acids were used to further constrain the origins of sedimentary OC. Short-chain n-C14-n-C18 fatty acids of algal origin were depleted in δ13C (δ13C -37.5 to -35.2 ‰) but were enriched in 14C (Δ14C > 0) compared to long-chain n-C24-n-C28 acids of vascular plant origins with higher δ13C (-33.0 to -31.0 ‰) but variable Δ14C values (-180 and 61 ‰). These data demonstrate the potentially complex source and age distributions found within river sediments and provide insights about sediment and organic matter supply to the Sacramento-San Joaquin River Delta.

Earthworm effects on the incorporation of litter C and N into soil organic matter in a sugar maple forest.

PubMed

Fahey, Timothy J; Yavitt, Joseph B; Sherman, Ruth E; Maerz, John C; Groffman, Peter M; Fisk, Melany C; Bohlen, Patrick J

2013-07-01

To examine the mechanisms of earthworm effects on forest soil C and N, we double-labeled leaf litter with 13C and 15N, applied it to sugar maple forest plots with and without earthworms, and traced isotopes into soil pools. The experimental design included forest plots with different earthworm community composition (dominated by Lumbricus terrestris or L. rubellus). Soil carbon pools were 37% lower in earthworm-invaded plots largely because of the elimination of the forest floor horizons, and mineral soil C:N was lower in earthworm plots despite the mixing of high C:N organic matter into soil by earthworms. Litter disappearance over the first winter-spring was highest in the L. terrestris (T) plots, but during the warm season, rapid loss of litter was observed in both L. rubellus (R) and T plots. After two years, 22.0% +/- 5.4% of 13C released from litter was recovered in soil with no significant differences among plots. Total recovery of added 13C (decaying litter plus soil) was much higher in no-worm (NW) plots (61-68%) than in R and T plots (20-29%) as much of the litter remained in the former whereas it had disappeared in the latter. Much higher percentage recovery of 15N than 13C was observed, with significantly lower values for T than R and NW plots. Higher overwinter earthworm activity in T plots contributed to lower soil N recovery. In earthworm-invaded plots isotope enrichment was highest in macroaggregates and microaggregates whereas in NW plots silt plus clay fractions were most enriched. The net effect of litter mixing and priming of recalcitrant soil organic matter (SOM), stabilization of SOM in soil aggregates, and alteration of the soil microbial community by earthworm activity results in loss of SOM and lowering of the C:N ratio. We suggest that earthworm stoichiometry plays a fundamental role in regulating C and N dynamics of forest SOM.

Conformational heterogeneity in the C-terminal zinc fingers of human MTF-1: an NMR and zinc-binding study.

PubMed

Giedroc, D P; Chen, X; Pennella, M A; LiWang, A C

2001-11-09

The human metalloregulatory transcription factor, metal-response element (MRE)-binding transcription factor-1 (MTF-1), contains six TFIIIA-type Cys(2)-His(2) motifs, each of which was projected to form well-structured betabetaalpha domains upon Zn(II) binding. In this report, the structure and backbone dynamics of a fragment containing the unusual C-terminal fingers F4-F6 has been investigated. (15)N heteronuclear single quantum coherence (HSQC) spectra of uniformly (15)N-labeled hMTF-zf46 show that Zn(II) induces the folding of hMTF-zf46. Analysis of the secondary structure of Zn(3) hMTF-zf46 determined by (13)Calpha chemical shift indexing and the magnitude of (3)J(Halpha-HN) clearly reveal that zinc fingers F4 and F6 adopt typical betabetaalpha structures. An analysis of the heteronuclear backbone (15)N relaxation dynamics behavior is consistent with this picture and further reveals independent tumbling of the finger domains in solution. Titration of apo-MTF-zf46 with Zn(II) reveals that the F4 domain binds Zn(II) significantly more tightly than do the other two finger domains. In contrast to fingers F4 and F6, the betabetaalpha fold of finger F5 is unstable and only partially populated at substoichiometric Zn(II); a slight molar excess of zinc results in severe conformational exchange broadening of all F5 NH cross-peaks. Finally, although Cd(II) binds to apo-hMTF-zf46 as revealed by intense S(-)-->Cd(II) absorption, a non-native structure results; addition of stoichiometric Zn(II) to the Cd(II) complex results in quantitative refolding of the betabetaalpha structure in F4 and F6. The functional implications of these results are discussed.

Space-Time Adaptive Processing for Airborne Radar

DTIC Science & Technology

1994-12-13

horizontal plane Uniform linear antenna array (possibly columns of a planar array) Identical element patterns 13 14 15 9 7 7,33 7 7 Target Model ...Parameters for Example Scenario 31 3 Assumptions Made for Radar System and Signal Model 52 4 Platform and Interference Scenario for Baseline Scenario. 61 5...pulses, is addressed first. Fully adaptive STAP requires the solution to a system of linear equations of size MN, where N is the number of array

Characterizing Variation of Isotopic Markers in Northern Alaskan Caribou Forages

NASA Astrophysics Data System (ADS)

VanSomeren, L.; Barboza, P. S.; Gustine, D. D.; Parrett, L. S.; Stricker, C. A.

2013-12-01

Isotopic markers in feces and tissues are a potential tool for monitoring the importance of feeding areas for migratory herbivores such as caribou (Rangifer tarandus). Many of these techniques are currently limited by gaps in our knowledge of how these isotopic signatures vary over the landscape. We collected seven species of preferred caribou forages along a latitudinal gradient in the summer ranges of the Central Arctic (9 sites) and Teshekpuk Lake (4 sites) caribou herds during 2011 and 2012. We analyzed forages at peak protein content and at the end of the season to characterize temporal, species-specific, and spatial variation in isotopic markers. The availability of C and N was measured by digestion in vitro. Isotopic signatures of digested samples were used to calculate fractionation that would bias the isotopic signature of feces. The range of values for isotopes (all values ‰) of nitrogen (δ15N -9.5 - +4.3), and sulfur (δ34S -3.6 - +15.5) were greater than those for carbon (δ13C -30.5 - -24.9). Small declines in forage δ13C with latitude (Carex aquatilis, Eriophorum vaginatum, Salix pulchra, and S. richardsonii [all P < 0.01]), season (all species except C. bigelowii [all P ≤ 0.01]), and season x year (S. richardsonii; P = 0.01) were probably associated with changes in water availability. Fractionation of δ13C in early season forages was 0.1 × 1.0 and positively related to C availability (58% × 15%; P < 0.01) with the greatest fractionation for the highly digestible forb Pedicularis langsdorfii (1.43 × 0.44; P < 0.01). Sedges (Carex and Eriophorum) were significantly higher in δ15N than Salix spp. and other dicots (2.0 × 1.1 vs. -2.9 × 2.2; P < 0.01). For Salix spp., δ15N was consistent over the season and between years. Fractionation of δ15N in early season forages was 0.2 × 1.8 and not related to N availability (60% × 17%). For S. pulchra, δ34S may indicate usage of coastal habitats over foothills because δ34S was higher on the coastal plain than in the foothills (11.1 × 3.3 and 3.1 × 2.6; P < 0.01). Isotopic ratios in N and S show the greatest promise for tracking diet and location of migratory caribou whereas the narrow range in δ13C is affected by species, season and location.

pH-dependent equilibrium isotope fractionation associated with the compound specific nitrogen and carbon isotope analysis of substituted anilines by SPME-GC/IRMS.

PubMed

Skarpeli-Liati, Marita; Turgeon, Aurora; Garr, Ashley N; Arnold, William A; Cramer, Christopher J; Hofstetter, Thomas B

2011-03-01

Solid-phase microextraction (SPME) coupled to gas chromatography/isotope ratio mass spectrometry (GC/IRMS) was used to elucidate the effects of N-atom protonation on the analysis of N and C isotope signatures of selected aromatic amines. Precise and accurate isotope ratios were measured using polydimethylsiloxane/divinylbenzene (PDMS/DVB) as the SPME fiber material at solution pH-values that exceeded the pK(a) of the substituted aniline's conjugate acid by two pH-units. Deviations of δ(15)N and δ(13)C-values from reference measurements by elemental analyzer IRMS were small (<0.9‰) and within the typical uncertainties of isotope ratio measurements by SPME-GC/IRMS. Under these conditions, the detection limits for accurate isotope ratio measurements were between 0.64 and 2.1 mg L(-1) for δ(15)N and between 0.13 and 0.54 mg L(-1) for δ(13)C, respectively. Substantial inverse N isotope fractionation was observed by SPME-GC/IRMS as the fraction of protonated species increased with decreasing pH leading to deviations of -20‰ while the corresponding δ(13)C-values were largely invariant. From isotope ratio analysis at different solution pHs and theoretical calculations by density functional theory, we derived equilibrium isotope effects, EIEs, pertinent to aromatic amine protonation of 0.980 and 1.001 for N and C, respectively, which were very similar for all compounds investigated. Our work shows that N-atom protonation can compromise accurate compound-specific N isotope analysis of aromatic amines.

Pyruvate carboxylase is critical for non–small-cell lung cancer proliferation

PubMed Central

Sellers, Katherine; Fox, Matthew P.; Bousamra, Michael; Slone, Stephen P.; Higashi, Richard M.; Miller, Donald M.; Wang, Yali; Yan, Jun; Yuneva, Mariia O.; Deshpande, Rahul; Lane, Andrew N.; Fan, Teresa W.-M.

2015-01-01

Anabolic biosynthesis requires precursors supplied by the Krebs cycle, which in turn requires anaplerosis to replenish precursor intermediates. The major anaplerotic sources are pyruvate and glutamine, which require the activity of pyruvate carboxylase (PC) and glutaminase 1 (GLS1), respectively. Due to their rapid proliferation, cancer cells have increased anabolic and energy demands; however, different cancer cell types exhibit differential requirements for PC- and GLS-mediated pathways for anaplerosis and cell proliferation. Here, we infused patients with early-stage non–small-cell lung cancer (NSCLC) with uniformly 13C-labeled glucose before tissue resection and determined that the cancerous tissues in these patients had enhanced PC activity. Freshly resected paired lung tissue slices cultured in 13C6-glucose or 13C5,15N2-glutamine tracers confirmed selective activation of PC over GLS in NSCLC. Compared with noncancerous tissues, PC expression was greatly enhanced in cancerous tissues, whereas GLS1 expression showed no trend. Moreover, immunohistochemical analysis of paired lung tissues showed PC overexpression in cancer cells rather than in stromal cells of tumor tissues. PC knockdown induced multinucleation, decreased cell proliferation and colony formation in human NSCLC cells, and reduced tumor growth in a mouse xenograft model. Growth inhibition was accompanied by perturbed Krebs cycle activity, inhibition of lipid and nucleotide biosynthesis, and altered glutathione homeostasis. These findings indicate that PC-mediated anaplerosis in early-stage NSCLC is required for tumor survival and proliferation. PMID:25607840

Testing compound-specific δ13C of amino acids in mussels as a new approach to determine the average 13C values of primary production in littoral ecosystems

NASA Astrophysics Data System (ADS)

Vokhshoori, N. L.; Larsen, T.; McCarthy, M.

2012-12-01

Compound-specific isotope analysis of amino acids (CSI-AA) is a technique used to decouple trophic enrichment patterns from source changes at the base of the food web. With this new emerging tool, it is possible to precisely determine both trophic position and δ15N or δ13C source values in higher feeding organisms. While most work to date has focused on nitrogen (N) isotopic values, early work has suggested that δ13C CSI-AA has great potential as a new tracer both to a record δ13C values of primary production (unaltered by trophic transfers), and also to "fingerprint" specific carbon source organisms. Since essential amino acids (EAA) cannot be made de novo in metazoans but must be obtained from diet, the δ13C value of the primary producer is preserved through the food web. Therefore, the δ13C values of EAAs act as a unique signature of different primary producers and can be used to fingerprint the dominant carbon (C) source driving primary production at the base of the food web. In littoral ecosystems, such as the California Upwelling System (CUS), the likely dominant C sources of suspended particulate organic matter (POM) pool are kelp, upwelling phytoplankton or estuarine phytoplankton. While bulk isotopes of C and N are used extensively to resolve relative consumer hierarchy or shifting diet in a food web, we found that the δ13C bulk values in mussels cannot distinguish exact source in littoral ecosystems. Here we show 15 sites within the CUS, between Cape Blanco, OR and La Jolla, CA where mussels were sampled and analyzed for both bulk δ13C and CSI-AA. We found no latitudinal trends, but rather average bulk δ13C values for the entire coastal record were highly consistent (-15.7 ± 0.9‰). The bulk record would suggest either nutrient provisioning from kelp or upwelled phytoplankton, but 13C-AA fingerprinting confines these two sources to upwelling. This suggests that mussels are recording integrated coastal phytoplankton values, with the enriched δ13C values likely linked to nearshore processes in the CA upwelling zone. Overall, these results clearly demonstrate, for the first time, the dual potential of δ13C CSI-AA to simultaneously indicate δ13C values of primary production, as well as to narrow major primary production sources. Our results suggest that, when applied to littoral filter feeders or other bio or paleo-archives, δ13C CSI-AA represents a new tool for reconstructing past perturbations to the marine carbon cycle.

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

NASA Astrophysics Data System (ADS)

Ding, Keyang; Gronenborn, Angela M.

2004-04-01

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

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

NASA Technical Reports Server (NTRS)

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

1984-01-01

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

Fate of microbial nitrogen, carbon, hydrolysable amino acids, monosaccharides, and fatty acids in sediment

NASA Astrophysics Data System (ADS)

Veuger, Bart; van Oevelen, Dick; Middelburg, Jack J.

2012-04-01

The fate of microbial carbon, nitrogen, hydrolysable amino acids (HAAs), monosaccharides, and fatty acids in sediment was investigated experimentally. The microbial community of a tidal flat sediment was labeled with 13C-enriched glucose and 15N-enriched ammonium, and sediment was incubated for up to 371 days. Analysis of total concentrations and 13C- and 15N content of bulk sediment, hydrolysable amino acids (including D-alanine), monosaccharides, total fatty acids (TFAs), and phospholipid-derived fatty acids (PLFAs) allowed us to trace the fate of microbial biomass and -detritus and the major biochemical groups therein (proteins, carbohydrates, and lipids) over intermediate time scales (weeks-months). Moreover, the unidentified fraction of the labeled material (i.e. not analyzed as HAA, FA, or carbohydrate) provided information on the formation and fate of molecularly uncharacterizable organic matter. Loss of 13C and 15N from the sediment was slow (half live of 433 days) which may have been due to the permanently anoxic conditions in the experiment. Loss rates for the different biochemical groups were also low with the following order of loss rate constants: PLFA > TFA > HAA > monosaccharides. The unidentified 13C-pool was rapidly formed (within days) and then decreased relatively slowly, resulting in a gradual relative accumulation of this pool over time. Degradation and microbial reworking of the labeled material resulted in subtle, yet consistent, diagenetic changes within the different biochemical groups. In the HAA pool, glycine, lysine, and proline were lost relatively slowly (i.e. best preserved) while there was no accumulation of D-alanine relative to L-alanine, indicating no relative accumulation of bacterial macromolecules rich in D-alanine. In the fatty acid pool, there was very little difference between PLFAs and TFAs, indicating a very similar lability of these pools. Differences between individual fatty acids included a relatively slow loss of i15:0, ai15:0 and 18:1ω7c which likely resulted from production of these bacterial fatty acids during bacterial reworking of the organic matter. Differences between loss rate constants for individual monosaccharides were not significant. An exception was ribose that was produced and lost relatively rapidly, which may be related to ribose being an important component of RNA. Losses of bulk 13C and 15N were closely coupled despite partly being present in different biochemicals and partly being derived from different microbial sources, indicating no selective preservation of either C or N during organic matter diagenesis.

Chaetognatha of the Namibian Upwelling Region: Taxonomy, Distribution and Trophic Position

PubMed Central

Bohata, Karolina; Koppelmann, Rolf

2013-01-01

In October 2010, the vertical distribution, biodiversity and maturity stages of Chaetognatha species were investigated at four stations located off Walvis Bay, Namibia. Seventeen species were detected and classified as pelagic, shallow-mesopelagic, deep-mesopelagic and bathypelagic species based upon the weighted mean depth derived from their average vertical distribution. High abundances of Chaetognatha were found in the upper 100 m at all stations of the Walvis Bay transect with a maximum value of 20837 ind. 1000 m−3 at the outer shelf station near the surface. The community was dominated by species of the Serratodentata group. Furthermore, the distribution of Chaetognatha did not seem to be influenced by low oxygen concentrations. Stable isotope ratios of carbon and nitrogen in Chaetognatha were determined for seven different areas located off northern Namibia. The values of δ15N ranged from 6.05 ‰ to 11.39 ‰, while the δ13C values varied between −23.89 ‰ and −17.03 ‰. The highest values for δ15N were observed at the Walvis Bay shelf break station. The lowest δ13C values were found at the Rocky Point offshore station, which was statistically different from all other areas. Stable isotopes of carbon and nitrogen were determined for four taxa (Sagitta minima, Planctonis group, Sagitta enflata, Sagitta decipiens). In this case, the δ15N values ranged from 6.17 ‰ to 10.38 ‰, whereas the δ13C values varied from −22.70 ‰ to −21.56 ‰. The lowest δ15N values were found for S. minima. The C- and N-content revealed maximum C-values for S. decipiens and maximum N-values for the Planctonis group. The C:N ratio of Chaetognatha ranged between 5.25 and 6.20. Overall, Chaetognatha are a diverse group in the pelagic food web of the Benguela Upwelling System and act as competitors of fish larvae and jelly fish by preying on copepods. PMID:23342016

Contribution of petroleum-derived organic carbon to sedimentary organic carbon pool in the eastern Yellow Sea (the northwestern Pacific).

PubMed

Kim, Jung-Hyun; Lee, Dong-Hun; Yoon, Suk-Hee; Jeong, Kap-Sik; Choi, Bohyung; Shin, Kyung-Hoon

2017-02-01

We investigated molecular distributions and stable carbon isotopic compositions (δ 13 C) of sedimentary n-alkanes (C 15 C 35 ) in the riverbank and marine surface sediments to trace natural and anthropogenic organic carbon (OC) sources in the eastern Yellow Sea which is a river dominated marginal sea. Molecular distributions of n-alkanes are overall dominated by odd-carbon-numbered high molecular weight n-C 27 , n-C 29 , and n-C 31 . The δ 13 C signatures of n-C 27 , n-C 29 , and n-C 31 indicate a large contribution of C 3 gymnosperms as the main source of n-alkanes, with the values of -29.5 ± 1.3‰, -30.3 ± 2.0‰, and -30.0 ± 1.7‰, respectively. However, the contribution of thermally matured petroleum-derived OC to the sedimentary OC pool is also evident, especially in the southern part of the study area as shown by the low carbon preference index (CPI 25-33 , <1) and natural n-alkanes ratio (NAR, <-0.6) values. Notably, the even-carbon-numbered long-chain n-C 28 and n-C 30 in this area have higher δ 13 C values (-26.2 ± 1.5‰ and -26.5 ± 1.9‰, respectively) than the odd-carbon-numbered long-chain n-C 29 and n-C 31 (-28.4 ± 2.7‰ and -28.4 ± 2.4‰, respectively), confirming two different sources of long-chain n-alkanes. Hence, our results highlight a possible influence of petroleum-induced OC on benthic food webs in this ecosystem. However, the relative proportions of the natural and petroleum-derived OC sources are not calculated due to the lack of biogeochemical end-member data in the study area. Hence, more works are needed to constrain the end-member values of the organic material supplied from the rivers to the eastern Yellow Sea and thus to better understand the source and depositional process of sedimentary OC in the eastern Yellow Sea. Copyright © 2016 Elsevier Ltd. All rights reserved.

Reduction in lipoprotein-associated apoC-III levels following volanesorsen therapy: phase 2 randomized trial results.

PubMed

Yang, Xiaohong; Lee, Sang-Rok; Choi, Yun-Seok; Alexander, Veronica J; Digenio, Andres; Yang, Qingqing; Miller, Yury I; Witztum, Joseph L; Tsimikas, Sotirios

2016-04-01

Elevated apoC-III levels predict increased cardiovascular risk when present on LDL and HDL particles. We developed novel high-throughput chemiluminescent ELISAs that capture apoB, lipoprotein (a) [Lp(a)], and apoA-I in plasma and then detect apoC-III on these individual lipoproteins as apoCIII-apoB, apoCIII-Lp(a), and apoCIII-apoAI complexes, respectively. We assessed the effects on these complexes of placebo or 100-300 mg volanesorsen, a generation 2.0+ antisense drug that targets apoC3 mRNA in patients with hypertriglyceridemia, including familial chylomicronemia syndrome (n = 3), volanesorsen monotherapy (n = 51), and as add-on to fibrate (n = 26), treated for 85 days and followed for 176 days. Compared with placebo, volanesorsen was associated with an 82.3 ± 11.7%, 81.3 ± 15.7%, and 80.8 ± 13.6% reduction in apoCIII-apoB, apoCIII-Lp(a), and apoCIII-apoA-I, respectively (300 mg dose;P< 0.001 for all), at day 92. Strong correlations in all assay measures were noted with total plasma apoC-III, chylomicron-apoC-III, and VLDL-apoC-III. In conclusion, novel high-throughput ELISAs were developed to detect lipoprotein-associated apoC-III, including for the first time on Lp(a). Volanesorsen uniformly lowers apoC-III on apoB-100, Lp(a), and apoA-I lipoproteins, and may be a potent agent to reduce triglycerides and cardiovascular risk mediated by apoC-III. Copyright © 2016 by the American Society for Biochemistry and Molecular Biology, Inc.

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.

The evaluation of a new method to extract spectroscopic factors using asymptotic normalization coefficients and the astrophysical ^14C(n,γ)^15C reaction rate

NASA Astrophysics Data System (ADS)

McCleskey, M.; Mukhamedzhanov, A. M.; Trache, L.; Banu, A.; Goldberg, V.; Roeder, B. T.; Simmons, E. N.; Spiridon, A.; Tribble, R. E.

2011-10-01

A new method to determine spectroscopic factors (SFs) that utilizes asymptotic normalization coefficients (ANCs) has been tested at Texas A&M, using ^15C as a test case. The method would use the ANC to fix the external contribution to a non-peripheral reaction which would otherwise be free to vary to unphysical values in a traditional approach. The investigation consisted of two parts. First, the ANC for the ^14C+n configuration in ^15C was determined from the heavy ion neutron transfer reaction ^13C(^14C,^15C)^12C and the inverse kinematics reaction d(^14C,p)^15C. Both of these reactions were measured at sufficiently low energy to be peripheral. Next, a non-peripheral reaction ^14C(d,p)^15C was measured with an incident deuteron energy of 60 MeV, and this reaction was used along with the previously determined ANC to attempt to find the SF. The ANC was also used to calculate the astrophysical neutron direct capture rate for ^14C(n,γ)^15C, which was compared with recent direct experimental results.

Trophic diversity in the evolution and community assembly of loricariid catfishes

PubMed Central

2012-01-01

Background The Neotropical catfish family Loricariidae contains over 830 species that display extraordinary variation in jaw morphologies but nonetheless reveal little interspecific variation from a generalized diet of detritus and algae. To investigate this paradox, we collected δ13C and δ15N stable isotope signatures from 649 specimens representing 32 loricariid genera and 82 species from 19 local assemblages distributed across South America. We calculated vectors representing the distance and direction of each specimen relative to the δ15N/δ13C centroid for its local assemblage, and then examined the evolutionary diversification of loricariids across assemblage isotope niche space by regressing the mean vector for each genus in each assemblage onto a phylogeny reconstructed from osteological characters. Results Loricariids displayed a total range of δ15N assemblage centroid deviation spanning 4.9‰, which is within the tissue–diet discrimination range known for Loricariidae, indicating that they feed at a similar trophic level and that δ15N largely reflects differences in their dietary protein content. Total range of δ13C deviation spanned 7.4‰, which is less than the minimum range reported for neotropical river fish communities, suggesting that loricariids selectively assimilate a restricted subset of the full basal resource spectrum available to fishes. Phylogenetic regression of assemblage centroid-standardized vectors for δ15N and δ13C revealed that loricariid genera with allopatric distributions in disjunct river basins partition basal resources in an evolutionarily conserved manner concordant with patterns of jaw morphological specialization and with evolutionary diversification via ecological radiation. Conclusions Trophic partitioning along elemental/nutritional gradients may provide an important mechanism of dietary segregation and evolutionary diversification among loricariids and perhaps other taxonomic groups of apparently generalist detritivores and herbivores. Evolutionary patterns among the Loricariidae show a high degree of trophic niche conservatism, indicating that evolutionary lineage affiliation can be a strong predictor of how basal consumers segregate trophic niche space. PMID:22835218

13C and 15N CP/MAS, 1H-15N SCT CP/MAS and FTIR spectroscopy as tools for qualitative detection of the presence of zwitterionic and non-ionic forms of ansa-macrolide 3-formylrifamycin SV and its derivatives in solid state.

PubMed

Przybylski, Piotr; Pyta, Krystian; Klich, Katarzyna; Schilf, Wojciech; Kamieński, Bohdan

2014-01-01

(13)C, (15)N CP/MAS, including (1)H-(13)C and (1)H-(15)N short contact time CP/MAS experiments, and FTIR methods were applied for detailed structural characterization of ansa-macrolides as 3-formylrifamycin SV (1) and its derivatives (2-6) in crystal and in powder forms. Although HPLC chromatograms for 2/CH3 OH and 2/CH3 CCl3 were the same for rifampicin crystals dissolved in respective solvents, the UV-vis data recorded for them were different in 300-375 nm region. Detailed solid state (13)C and (15)N CP/MAS NMR and FTIR studies revealed that rifampicin (2), in contrast to 3-formylrifamycin SV (1) and its amino derivatives (3-6), can occur in pure non-ionic or zwitterionic forms in crystal and in pure these forms or a mixture of them in a powder. Multinuclear CP/MAS and FTIR studies demonstrated also that 3-6 derivatives were present exclusively in pure zwitterionic forms, both in powder and in crystal. On the basis of the solid state NMR and FTIR studies, two conformers of 3-formylrifamycin SV were detected in powder form due to the different orientations of carbonyl group of amide moiety. The PM6 molecular modeling at the semi-empirical level of theory, allowed visualization the most energetically favorable non-ionic and zwitterionic forms of 1-6 antibiotics, strongly stabilized via intramolecular H-bonds. FTIR studies indicated that the originally adopted forms of these type antibiotics in crystal or in powder are stable in standard laboratory conditions in time. The results presented point to the fact that because of a possible presence of two forms of rifampicin (compound 2), quantification of the content of this antibiotic in relevant pharmaceuticals needs caution. Copyright © 2013 John Wiley & Sons, Ltd.

Continuous-Wave Cavity Ring-Down Spectroscopy in a Pulsed Uniform Supersonic Flow

NASA Astrophysics Data System (ADS)

Thawoos, Shameemah; Suas-David, Nicolas; Suits, Arthur

2017-06-01

We introduce a new approach that couples a pulsed uniform supersonic flow with high sensitivity continuous wave cavity ringdown spectroscopy (UF-CRDS) operated in the near infrared (NIR). This combination is related to the CRESU technique developed in France and used for many years to study reaction kinetics at low temperature, and to the microwave based chirped-pulse uniform supersonic flow spectrometer (CPUF) developed in our group which has successfully demonstrated the use of pulsed uniform supersonic flow to probe reaction dynamics at temperatures as low as 22 K. CRDS operated with NIR permits access to the first overtones of C-H and O-H stretching/bending which, in combination with its extraordinary sensitivity opens new experiments complementary to the CPUF technique. The UF-CRDS apparatus (Figure) utilizes the pulsed uniform flow produced by means of a piezo-electric stack valve in combination with a Laval nozzle. At present, two machined aluminum Laval nozzles designed for carrier gases Ar and He generate flows with a temperature of approximately 25 K and pressure around 0.15 mbar. This flow is probed by an external cavity diode laser in the NIR (1280-1380 nm). Laval nozzles designed using a newly developed MATLAB-based program will be used in the future. A detailed illustration of the novel UF-CRDS instrumentation and its performance will be presented along with future directions and applications. I. Sims, J. L. Queffelec, A. Defrance, C. Rebrion-Rowe, D. Travers, P. Bocherel, B. Rowe, I. W. Smith, J. Chem. Phys. 100, 4229-4241, (1994). C. Abeysekera, B. Joalland, N. Ariyasingha, L. N. Zack, I. R. Sims, R. W. Field, A. G. Suits, J. Phys. Chem. Lett. 6, 1599-1604, (2015). N. Suas-David, T. Vanfleteren, T. Foldes, S. Kassi, R. Georges, M. Herman, J. Phys. Chem.A, 119, 10022-10034, (2015). C. Abeysekera, B. Joalland, Y. Shi, A. Kamasah, J. M. Oldham, A. G. Suits, Rev. Sci. Instrum. 85, 116107, (2014).

Novel Imaging Contrast Methods for Hyperpolarized 13 C Magnetic Resonance Imaging

NASA Astrophysics Data System (ADS)

Reed, Galen Durant

Magnetic resonance imaging using hyperpolarized 13C-labeled small molecules has emerged as an extremely powerful tool for the in vivo monitoring of perfusion and metabolism. This work presents methods for improved imaging, parameter mapping, and image contrast generation for in vivo hyperpolarized 13C MRI. Angiography using hyperpolarized urea was greatly improved with a highly T2-weighted acquisition in combination with 15N labeling of the urea amide groups. This is due to the fact that the T2 of [13C]urea is strongly limited by the scalar coupling to the neighboring quadrupolar 14N. The long in vivo T2 values of [13C, 15N2]urea were utilized for sub-millimeter projection angiography using a contrast agent that could be safely injected in concentrations of 10-100 mM while still tolerated in patients with renal insufficiency. This study also presented the first method for in vivo T2 mapping of hyperpolarized 13C compounds. The in vivo T2 of urea was short in the blood and long within the kidneys. This persistent signal component was isolated to the renal filtrate, thus enabling for the first time direct detection of an imaging contrast agent undergoing glomerular filtration. While highly T2-weighted acquisitions select for molecules with short rotational correlation times, high diffusion weighting selects for those with the long translational correlation times. A specialized spin-echo EPI sequence was developed in order to generate highly diffusion-weighted hyperpolarized 13C images on a clinical MRI system operating within clinical peak- RF and gradient amplitude constraints. Low power adiabatic spin echo pulses were developed in order to generate a sufficiently large refocused bandwidth while maintaining low nominal power. This diffusion weighted acquisition gave enhanced tumor contrast-to-noise ratio when imaging [1-13C]lactate after infusion of [1-13C]pyruvate. Finally, the first in-man hyperpolarized 13C MRI clinical trial is discussed.

Linking stable isotopes and biochemical responses in Balanus glandula under sewage influence.

PubMed

Laitano, M V; Díaz-Jaramillo, M; Rodriguez, Y E; Ducós, E; Panarello, H O; Fernández-Gimenez, A V

2018-02-01

In the present study, we analyzed the influence of untreated sewage exposure on carbon (δ13C) and nitrogen (δ15N) isotopic composition and several biochemical responses in the barnacle Balanus glandula. The main objective was to evaluate whether changes in stable isotopes signature do reflect biochemical sub-lethal effects in a sewage influence gradient. Stable isotopes analysis showed differences in isotope signatures between close sewage influence and distant sites, being δ13C signatures stronger than that of δ15N. Regarding biochemical effects, although organisms close to the effluent would be clearly exposed to contaminants (increased GST activity) the oxidative stress would not be too evident (peroxidases and ACAP not affected). The most affected physiological aspect was the digestive one, reflected in increased alkaline proteases and lipases activities. A clear relation between δ15N and GST activity was found, showing to δ15N as an indicator of potential exposure to chemical contaminants.

Disentangling effects of growth and nutritional status on seabird stable isotope ratios.

PubMed

Sears, Justine; Hatch, Scott A; O'Brien, Diane M

2009-02-01

A growing number of studies suggest that an individual's physiology affects its carbon and nitrogen stable isotope signatures, obscuring a signal often assumed to be only a reflection of diet and foraging location. We examined effects of growth and moderate food restriction on red blood cell (RBC) and feather delta(15)N and delta(13)C in rhinoceros auklet chicks (Cerorhinca monocerata), a piscivorous seabird. Chicks were reared in captivity and fed either control (75 g/day; n = 7) or ~40% restricted (40 g/day; n = 6) amounts of high quality forage fish. We quantified effects of growth on isotopic fractionation by comparing delta(15)N and delta(13)C in control chicks to those of captive, non-growing subadult auklets (n = 11) fed the same diet. To estimate natural levels of isotopic variation, we also collected blood from a random sample of free-living rhinoceros auklet adults and chicks in the Gulf of Alaska (n = 15 for each), as well as adult feather samples (n = 13). In the captive experiment, moderate food restriction caused significant depletion in delta(15)N of both RBCs and feathers in treatment chicks compared to control chicks. Growth also induced depletion in RBC delta(15)N, with chicks exhibiting lower delta(15)N when they were growing the fastest. As growth slowed, delta(15)N increased, resulting in an overall pattern of enrichment over the course of the nestling period. Combined effects of growth and restriction depleted delta(15)N in chick RBCs by 0.92 per thousand. We propose that increased nitrogen-use efficiency is responsible for (15)N depletion in both growing and food-restricted chicks. delta(15)N values in RBCs of free-ranging auklets fell within a range of only 1.03 per thousand, while feather delta(15)N varied widely. Together, our captive and field results suggest that both growth and moderate food restriction can affect stable isotope ratios in an ecologically meaningful way in RBCs although not feathers due to greater natural variability in this tissue.

The structure and dynamics of rat apo-cellular retinol-binding protein II in solution: comparison with the X-ray structure.

PubMed

Lu, J; Lin, C L; Tang, C; Ponder, J W; Kao, J L; Cistola, D P; Li, E

1999-03-05

The structure and dynamics of rat apo-cellular retinol binding protein II (apo-CRBP II) in solution has been determined by multidimensional NMR analysis of uniformly enriched recombinant rat 13C, 15N-apo-CRBP II and 15N-apo-CRBP II. The final ensemble of 24 NMR structures has been calculated from 3274 conformational restraints or 24.4 restraints/residue. The average root-mean-square deviation of the backbone atoms for the final 24 structures relative to their mean structure is 1.06 A. Although the average solution structure is very similar to the crystal structure, it differs at the putative entrance to the binding cavity, which is formed by the helix-turn-helix motif, the betaC-betaD turn and the betaE-betaF turn. The mean coordinates of the main-chain atoms of amino acid residues 28-38 are displaced in the solution structure relative to the crystal structure. The side-chain of F58, located on the betaC-betaD turn, is reoriented such that it interacts with L37 and no longer blocks entry into the ligand-binding pocket. Residues 28-35, which form the second helix of the helix-turn-helix motif in the crystal structure, do not exhibit a helical conformation in the solution structure. The solution structure of apo-CRBP II exhibits discrete regions of backbone disorder which are most pronounced at residues 28-32, 37-38 and 73-76 in the betaE-betaF turn as evaluated by the consensus chemical shift index, the root-mean-square deviation, amide 1H exchange rates and 15N relaxation studies. These studies indicate that fluctuations in protein conformation occur on the microseconds to ms time-scale in these regions of the protein. Some of these exchange processes can be directly observed in the three-dimensional 15N-resolved NOESY spectrum. These results suggest that in solution, apo-CRBP II undergoes conformational changes on the microseconds to ms time-scale which result in increased access to the binding cavity. Copyright 1999 Academic Press.

Uplifting of palsa peatlands by permafrost identified by stable isotope depth profiles

NASA Astrophysics Data System (ADS)

Krüger, Jan Paul; Conen, Franz; Leifeld, Jens; Alewell, Christine

2015-04-01

Natural abundances of stable isotopes are a widespread tool to investigate biogeochemical processes in soils. Palsas are peatlands with an ice core and are common in the discontinuous permafrost region. Elevated parts of palsa peatlands, called hummocks, were uplifted by permafrost out of the influence of groundwater. Here we used the combination of δ15N values and C/N ratio along depth profiles to identify perturbation of these soils. In the years 2009 and 2012 we took in total 14 peat cores from hummocks in two palsa peatlands near Abisko, northern Sweden. Peat samples were analysed in 2 to 4 cm layers for stable isotope ratios and concentrations of C and N. The uplifting of the hummocks by permafrost could be detected by stable isotope depth patterns with the highest δ15N value at permafrost onset, a so-called turning point. Regression analyses indicated in 11 of 14 peat cores increasing δ15N values above and decreasing values below the turning point. This is in accordance with the depth patterns of δ13C values and C/N ratios in these palsa peatlands. Onset of permafrost aggradation identified by the highest δ15N value in the profile and calculated from peat accumulation rates show ages ranging from 80 to 545 years and indicate a mean (±SD) peat age at the turning points of 242 (±66) years for Stordalen and 365 (±53) years for Storflaket peatland. The mean peat ages at turning points are within the period of the Little Ice Age. Furthermore, we tested if the disturbance, in this case the uplifting of the peat material, can be displayed in the relation of δ15N and C/N ratio following the concept of Conen et al. (2013). In unperturbed sites soil δ15N values cover a relatively narrow range at any particular C/N ratio. Changes in N cycling, i.e. N loss or gain, results in the loss or gain of 15N depleted forms. This leads to larger or smaller δ15N values than usual at the observed C/N ratio. All, except one, turning point show a perturbation in the depth profile, with most of the adjacent sampling points also indicating perturbation. This perturbation shows the changes in N cycling, in this case N loss, from these depths due to permafrost aggradation. Deeper parts of some profiles at Stordalen peatland indicate with the same approach an N gain, maybe due to lateral N input to these nutrient poor ecosystems. Most of the uppermost samples in the δ15N depth profiles show no perturbation, potentially due to the adaptation of these soils to the new conditions. Both stable isotope (δ15N and δ13C) depth profiles are suitable to detect palsa uplifting by permafrost. The perturbation of the peat by uplifting as well as the potential nutrient input can be detected by δ15N when related to the C/N ratio. Conen, F., Yakutin, M. V., Carle, N., and Alewell, C. (2013): δ15N natural abundance may directly disclose perturbed soil when related to C:N ratio. Rapid Commun. Mass Spectrom. 27: 1101-1104.

Modular Air Defense Effectiveness Model, Program Documentation and User’s Guide. Volume II. MADEM Programmer Manual.

DTIC Science & Technology

1980-01-31

Nuclear Agency 13 NUMFIER OF PAGES Washington, D.C. 20305 534 14 MONITORING AGENCY NAME 8 ADDRESS(,! itI(reI t &,n, ( f n ... o.I.n. Offi,e) 15...Initialization 13 3. Storage Management 13 4. Event Control 14 E. Diagnostics 17 1. Debug Routines 17 2. Data Structure Display Routines 19 F . Software...Structures 71 1. Player Lists 72 2. C2 Trees 78 3. Passive Target List 86 F . RED Structures 89 1. Red Theater Commander 90 2. Potential Target List 98 3

Spatial and trophic preferences of jumbo squid Dosidicus gigas (D´Orbigny, 1835) in the central Gulf of California: ecological inferences using stable isotopes.

PubMed

Trasviña-Carrillo, L D; Hernández-Herrera, A; Torres-Rojas, Y E; Galván-Magaña, F; Sánchez-González, A; Aguíñiga-García, S

2018-04-26

The jumbo squid Dosidicus gigas is a fishery resource of considerable economic and ecological importance in the Mexican Pacific. Studies on its habitat preferences are needed to understand recent fluctuations in the species' abundance and availability. Stable isotope analysis allows us to infer ecological aspects such as spatial distribution and trophic preferences. We used an isotope ratio mass spectrometer, automated for carbonate analysis, and coupled to an elemental analyzer, to determine the isotopic composition of statoliths (δ 18 O and δ 13 C values) and beaks (δ 13 C and δ 15 N values) from 219 individuals caught over two fishing seasons (2007 and 2009) off the coast of Santa Rosalía, in the central Gulf of California. We used these isotopic ratios to assess variation in spatial and trophic preferences by sex, size, and fishing season. In the 2009 group, we observed significant differences in statolith δ 13 C values and beak δ 13 C and δ 15 N values between males and females. Between size groups, we observed significant differences in statolith δ 18 O and δ 13 C values in 2007 and in beak δ 13 C and δ 15 N values during both seasons. Both seasons were characterized by high overlap in δ 18 O and δ 13 C values between sexes and in 2009 between size groups. We observed low trophic overlap between sexes in 2009 and between size groups during both seasons. The isotopic ratios from statoliths and beaks indicate that D. gigas has changed its spatial and trophic preferences, a shift that is probably related to changes in the species diet. This intraspecific variation in preferences could be related to characteristics such as size, which may influence squid distribution preferences. This article is protected by copyright. All rights reserved.

Ammonia fixation by humic substances: A nitrogen-15 and carbon-13 NMR study

USGS Publications Warehouse

Thorn, K.A.; Mikita, M.A.

1992-01-01

The process of ammonia fixation has been studied in three well characterized and structurally diverse fulvic and humic acid samples. The Suwannee River fulvic acid, and the IHSS peat and leonardite humic acids, were reacted with 15N-labelled ammonium hydroxide, and analyzed by liquid phase 15N NMR spectrometry. Elemental analyses and liquid phase 13C NMR spectra also were recorded on the samples before and after reaction with ammonium hydroxide. The largest increase in percent nitrogen occurred with the Suwannee River fulvic acid, which had a nitrogen content of 0.88% before fixation and 3.17% after fixation. The 15N NMR spectra revealed that ammonia reacted similarly with all three samples, indicating that the functional groups which react with ammonia exist in structural configurations common to all three samples. The majority of nitrogcn incorporated into the samples appears to be in the form of indole and pyrrole nitrogen, followed by pyridine, pyrazine, amide and aminohydroquinone nitrogen. Chemical changes in the individual samples upon fixation could not be discerned from the 13C NMR spectra.

Stable isotopic composition of deep sea gorgonian corals (Primnoa spp.): a new archive of surface processes.

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

Sherwood, O A; Heikoop, J M; Scott, D B

2005-02-03

The deep-sea gorgonian coral Primnoa spp. lives in the Atlantic and Pacific Oceans at depths of 65-3200 m. This coral has an arborescent growth form with a skeletal axis composed of annual rings made from calcite and gorgonin. It has a lifespan of at least several hundred years. It has been suggested that isotopic profiles from the gorgonin fraction of the skeleton could be used to reconstruct long-term, annual-scale variations in surface productivity. We tested assumptions about the trophic level, intra-colony isotopic reproducibility, and preservation of isotopic signatures in a suite of modern and fossil specimens. Measurements of gorgonin {Delta}{supmore » 14}C and {delta}{sup 15}N indicate that Primnoa spp. feed mainly on zooplankton and/or sinking particulate organic matter (POM{sub SINK}), and not on suspended POM (POM{sub SUSP}) or dissolved organic carbon (DOC). Gorgonin {delta}{sup 13}C and {delta}{sup 15}N in specimens from NE Pacific shelf waters, NW Atlantic slope waters, the Sea of Japan, and a South Pacific (Southern Ocean sector) seamount were strongly correlated with Levitus 1994 surface apparent oxygen utilization (AOU; the best available measure of surface productivity), demonstrating coupling between skeletal isotopic ratios and biophysical processes in surface water. Time-series isotopic profiles from different sections along the same colony were identical for {delta}{sup 13}C, while {delta}{sup 15}N profiles became more dissimilar with increasing separation along the colony axis. Similarity in C:N, {delta}{sup 13}C and {delta}{sup 15}N between modern and fossil specimens suggest that isotopic signatures are preserved over millennial timescales. Finally, the utility of this new archive was demonstrated by reconstruction of 20th century bomb radiocarbon.« less

Evaluation of the organic matter sources using the δ13C composition of individual n-alkanes in sediments from Brazilian estuarine systems by GC/C/IRMS

NASA Astrophysics Data System (ADS)

Maioli, Otávio Luiz Gusso; de Oliveira, Cristiane Rossi; Dal Sasso, Marco Aurélio; Madureira, Luiz Augusto dos Santos; Azevedo, Débora de Almeida; de Aquino Neto, Francisco Radler

2012-12-01

The δ13C composition of individual n-alkanes (from C16 to C34) was measured from surface sediments of five Brazilian estuarine systems affected by different organic matter sources, such as harbor area, industries, urban centers and sugar cane crops, in order to determine the origins of the organic matter. The aliphatic hydrocarbon fraction was analyzed by gas chromatography-combustion-isotope ratio mass spectrometry (GC/C/IRMS). The levels of n-alkanes in the studied areas ranged from 0.34 to 18.14 μg kg-1, being relatively low in comparison to high polluted environments. The Carbon Preference Index (CPI) calculated in the C23-C34 range indicates that n-alkanes are mainly inherited from cuticular waxes of higher plants. The δ13C composition of all n-alkanes detected in the sediment samples ranged from -39.6 to -18.3‰ showing different sources for the studied estuarine systems. Through Principal Component Analysis (PCA) it was possible to verify the petrogenic influence in the n-alkane sources, especially in the Paraíba do Sul sediment samples. Differences up to 15‰ of the δ13C values between n-alkanes of odd and even carbon number (C26 and C27) also indicated mixture of petrogenic and biogenic sources in Paraíba do Sul River. High (less negative) δ13C n-alkane values of odd carbon number were obtained from two sampling sites located close to an ethanol plant, indicating residues discharge of sugar cane (C4 plant). Influence of C3 plants that are the main components of dense ombrophile forest was observed in the Itajaí-Açu sediments by the decrease of δ13C (about 10‰ compared to the Paraíba do Sul River δ13C).

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

NASA Astrophysics Data System (ADS)

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

2015-07-01

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

Nuclear magnetic resonance (NMR) studies on the biosynthesis of fusaric acid from Fusarium oxysporum f. sp. vasinfectum.

PubMed

Stipanovic, Robert D; Wheeler, Michael H; Puckhaber, Lorraine S; Liu, Jinggao; Bell, Alois A; Williams, Howard J

2011-05-25

Fusarium oxysporum is a fungal pathogen that attacks many important plants. Uniquely pathogenic strains of F. oxysporum f. sp. vasinfectum were inadvertently imported into the United States on live cottonseed for dairy cattle feed. These strains produce exceptionally high concentrations of the phytotoxin fusaric acid. Thus, fusaric acid may be a critical component in the pathogenicity of these biotypes. This study investigated the biosynthesis of fusaric acid using (13)C-labeled substrates including [1,2-(13)C(2)]acetate as well as (13)C- and (15)N-labeled aspartate and [(15)N]glutamine. The incorporation of labeled substrates is consistent with the biosynthesis of fusaric acid from three acetate units at C5-C6, C7-C8, and C9-C10, with the remaining carbons being derived from aspartate via oxaloacetate and the TCA cycle; the oxaloacetate originates in part by transamination of aspartate, but most of the oxaloacetate is derived by deamination of aspartate to fumarate by aspartase. The nitrogen from glutamine is more readily incorporated into fusaric acid than that from aspartate.

Experimental and calculated 1H, 13C, 15N NMR spectra of famotidine

NASA Astrophysics Data System (ADS)

Barańska, M.; Czarniecki, K.; Proniewicz, L. M.

2001-05-01

Famotidine, 3-[[[2-[(aminoiminomethyl)amino]-4-thiazolyl]methyl]thio]- N-(aminosulfonyl), is a histamine H 2-receptor blocker that has been used mainly for the treatment of peptic ulcers and the Zollinger-Ellison syndrome. Its NMR spectra in different solvents were reported earlier; however, detailed interpretation has not been done thus far. In this work, experimental 1H, 13C and 15N NMR spectra of famotidine dissolved in DMSO-d 6 are shown. The assignment of observed chemical shifts is based on quantum chemical calculation at the Hartree-Fock/6-31G ∗ level. The geometry optimization of the famotidine molecule with two internal hydrogen bonds, i.e. [N(3)-H(23)⋯N(9) and N(3)⋯H(34)-N(20)], is done by using the B3LYP method with the 6-31G ∗ basis set.

Variability in the bulk composition and abundance of dissolved organic matter in the lower Mississippi and Pearl rivers

NASA Astrophysics Data System (ADS)

Duan, Shuiwang; Bianchi, Thomas S.; Shiller, Alan M.; Dria, Karl; Hatcher, Patrick G.; Carman, Kevin R.

2007-06-01

In this study, we examined the temporal and spatial variability of dissolved organic matter (DOM) abundance and composition in the lower Mississippi and Pearl rivers and effects of human and natural influences. In particular, we looked at bulk C/N ratio, stable isotopes (δ15N and δ13C) and 13C nuclear magnetic resonance (NMR) spectrometry of high molecular weight (HMW; 0.2 μm to 1 kDa) DOM. Monthly water samples were collected at one station in each river from August 2001 to 2003. Surveys of spatial variability of total dissolved organic carbon (DOC) and nitrogen (DON) were also conducted in June 2003, from 390 km downstream in the Mississippi River and from Jackson to Stennis Space Center in the Pearl River. Higher DOC (336-1170 μM), C/N ratio,% aromaticity, and more depleted δ15N (0.76-2.1‰) were observed in the Pearl than in the lower Mississippi River (223-380 μM, 4.7-11.5‰, respectively). DOC, C/N ratio, δ13C, δ15N, and % aromaticity of Pearl River HMW DOM were correlated with water discharge, which indicated a coupling between local soil inputs and regional precipitation events. Conversely, seasonal variability in the lower Mississippi River was more controlled by spatial variability of a larger integrative signal from the watershed as well as in situ DOM processing. Spatially, very little change occurred in total DOC in the downstream survey of the lower Mississippi River, compared to a decrease of 24% in the Pearl River. Differences in DOM between these two rivers were reflective of the Mississippi River having more extensive river processing of terrestrial DOM, more phytoplankton inputs, and greater anthropogenic perturbation than the Pearl River.

Necessity of Removing American Football Uniforms From Humans With Hyperthermia Before Cold-Water Immersion

PubMed Central

Miller, Kevin C.; Long, Blaine C.; Edwards, Jeffrey

2015-01-01

Context  The National Athletic Trainers' Association and the American College of Sports Medicine have recommended removing American football uniforms from athletes with exertional heat stroke before cold-water immersion (CWI) based on the assumption that the uniform impedes rectal temperature (Trec) cooling. Few experimental data exist to verify or disprove this assumption and the recommendations. Objectives  To compare CWI durations, Trec cooling rates, thermal sensation, intensity of environmental symptoms, and onset of shivering when hyperthermic participants wore football uniforms during CWI or removed the uniforms immediately before CWI. Design  Crossover study. Setting  Laboratory. Patients or Other Participants  Eighteen hydrated, physically active men (age = 22 ± 2 years, height = 182.5 ± 6.1 cm, mass = 85.4 ± 13.4 kg, body fat = 11% ± 5%, body surface area = 2.1 ± 0.2 m2) volunteered. Intervention(s)  On 2 days, participants exercised in the heat (approximately 40°C, approximately 40% relative humidity) while wearing a full American football uniform (shoes; crew socks; undergarments; shorts; game pants; undershirt; shoulder pads; jersey; helmet; and padding over the thighs, knees, hips, and tailbone [PADS]) until Trec reached 39.5°C. Next, participants immersed themselves in water that was approximately 10°C while wearing either undergarments, shorts, and crew socks (NOpads) or PADS without shoes until Trec reached 38°C. Main Outcome Measure(s)  The CWI duration (minutes) and Trec cooling rates (°C/min). Results  Participants had similar exercise times (NOpads = 40.8 ± 4.9 minutes, PADS = 43.2 ± 4.1 minutes; t17 = 2.0, P = .10), hypohydration levels (NOpads = 1.5% ± 0.3%, PADS = 1.6% ± 0.4%; t17 = 1.3, P = .22), and thermal-sensation ratings (NOpads = 7.2 ± 0.3, PADS = 7.1 ± 0.5; P > .05) before CWI. The CWI duration (median [interquartile range]; NOpads = 6.0 [5.4] minutes, PADS = 7.3 [9.8] minutes; z = 2.3, P = .01) and Trec cooling rates (NOpads = 0.28°C/min ± 0.14°C/min, PADS = 0.21°C/min ± 0.11°C/min; t17 = 2.2, P = .02) differed between uniform conditions. Conclusions  Whereas participants cooled faster in NOpads, we still considered the PADS cooling rate to be acceptable (ie, >0.16°C/min). Therefore, if clinicians experience difficulty removing PADS or CWI treatment is delayed, they may immerse fully equipped hyperthermic football players in CWI and maintain acceptable Trec cooling rates. Otherwise, PADS should be removed preimmersion to ensure faster body core temperature cooling. PMID:26678288

Stable isotope laser spectrometer for exploration of Mars.

PubMed

Sauke, T B; Becker, J F

1998-01-01

On Earth, measurements of the ratios of stable carbon isotopes have provided much information about geological and biological processes. For example, fractionation of carbon occurs in biotic processes and the retention of a distinctive 2-4% contrast in 13C/12C 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 13C/12C and 15N/14N measurements. Gas samples for measurement are to be produced by pyrolysis using soil samples as small as 50 mg. Measurements of 13C/12C, 18O/16O and 15N/14N 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 (<0.001 cm(-1)) has favorable features in comparison to mass spectrometry, the standard method of accurate isotopic ratio measurement. The miniature instrument could be ready to deploy on the 2003 or other Mars lander missions.

Using Stable Isotope Compositions of Animal Tissues to Infer Trophic Interactions in Gulf of Mexico Lower Slope Seep Communities

PubMed Central

Becker, Erin L.; Cordes, Erik E.; Macko, Stephen A.; Lee, Raymond W.; Fisher, Charles R.

2013-01-01

We analyzed the tissue carbon, nitrogen, and sulfur stable isotope contents of macrofaunal communities associated with vestimentiferan tubeworms and bathymodiolin mussels from the Gulf of Mexico lower continental slope (970-2800 m). Shrimp in the genus Alvinocaris associated with vestimentiferans from shallow (530 m) and deep (1400-2800 m) sites were used to test the hypothesis that seep animals derive a greater proportion of their nutrition from seeps (i.e. a lower proportion from the surface) at greater depths. To account for spatial variability in the inorganic source pool, we used the differences between the mean tissue δ13C and δ15N of the shrimp in each collection and the mean δ 13C and δ15N values of the vestimentiferans from the same collection, since vestimentiferans are functionally autotrophic and serve as a baseline for environmental isotopic variation. There was a significant negative relationship between this difference and depth for both δ13C and δ15N (p=0.02 and 0.007, respectively), which supports the hypothesis of higher dependence on seep nutrition with depth. The small polychaete worm Protomystides sp. was hypothesized to be a blood parasite of the vestimentiferan Escarpialaminata . There was a highly significant linear relationship between the δ13C values of Protomystides sp. and the E . laminata individuals to which they were attached across all collections (p < 0.001) and within a single collection (p = 0.01), although this relationship was not significant for δ15N and δ34S. We made several other qualitative inferences with respect to the feeding biology of the taxa occurring in these lower slope seeps, some of which have not been described prior to this study. PMID:24324572

Evidence for Dietary Time Series in Layers of Cetacean Skin Using Stable Carbon and Nitrogen Isotope Ratios.

PubMed

Wild, Lauren A; Chenoweth, Ellen M; Mueter, Franz J; Straley, Janice M

2018-05-18

Stable isotope analysis integrates diet information over a time period specific to the type of tissue sampled. For metabolically active skin of free-ranging cetaceans, cells are generated at the basal layer of the skin and migrate outward until they eventually slough off, suggesting potential for a dietary time series. Skin samples from cetaceans were analyzed using continuous-flow elemental analyzer isotope ratio mass spectrometery (EA-IRMS). We used ANOVAs to compare the variability of δ 13 C and δ 15 N values within and among layers and columns ("cores") of the skin of a fin, humpback, and sperm whale. We then used mixed-effects models to analyze isotopic variability among layers of 28 sperm whale skin samples, over the course of a season and among years. We found layer to be a significant predictor of δ 13 C values in the sperm whale's skin, and δ 15 N values the humpback whale's skin. There was no evidence for significant differences in δ 15 N or δ 13 C values among cores for any species. Mixed effects models selected layer and day of the year as significant predictors of δ 13 C and δ 15 N values in sperm whale skin across individuals sampled during the summer months in the Gulf of Alaska. These results suggest that skin samples from cetaceans may be subsampled to reflect diet during a narrower time period; specifically different layers of skin may contain a dietary time series. This underscores the importance of selecting an appropriate portion of skin to analyze based on the species and objectives of the study. This article is protected by copyright. All rights reserved.

Stable isotope patterns in micronekton from the Mozambique Channel

NASA Astrophysics Data System (ADS)

Ménard, Frédéric; Benivary, Hermann Doris; Bodin, Nathalie; Coffineau, Nathalie; Le Loc'h, François; Mison, Thomas; Richard, Pierre; Potier, Michel

2014-02-01

We measured the stable carbon (δ13C) and nitrogen (δ15N) isotopic composition of tissues of micronektonic organisms (fishes, squids, crustaceans and gelatinous organisms) collected in the Mozambique Channel during two scientific cruises in 2008 and 2009. The oceanic circulation in the Mozambique Channel is dominated by mesoscale cyclonic and anticyclonic eddies which play a key role in biological processes of less-productive deep-sea ecosystems. We investigated the potential impact of mesoscale features on the δ13C and δ15N values of 32 taxa of micronekton. Fishes, squids, crustaceans and gelatinous organisms encompassed a wide range of isotopic niches, with large overlaps among species. Our results showed that mesoscale features did not really influence the isotopic signatures of the sampled organisms, although cyclonic eddies can occasionally impact the nitrogen signatures of micronekton. We show that δ13C values were intermediate between standard offshore and nearshore signatures, suggesting that pelagic production in the Mozambique Channel could be partly supported by the transport and export of inorganic and organic particles from the Mozambican coast toward the offshore area. Trophic levels calculated from δ15N values ranged from 2.6 to 4.2, showing that micronekton taxa can be tertiary consumers in the Mozambique Channel. Our findings evidenced clusters of micronektonic organisms according to their δ15N or δ13C isotopic signatures, but variations in stable isotope values reflect a complex set of embedded processes linked to physical mesoscale dynamics (rotational dynamics of eddies) and basic biology and ecology of micronektonic organisms (vertical habitat, migration pattern, dietary habits, body length) that are discussed with regard to the stable isotope method based on time-integrated assimilated food.

Stable Isotopes (δ13C and δ15N) in Two Depth-Segregated Species of Deep-Sea Gorgonian Octocorals from the Eastern Pacific

NASA Astrophysics Data System (ADS)

Barnes, S.; Williams, B.; Etnoyer, P. J.

2016-02-01

Found across the world's oceans and with ages up to hundreds of years, deep-sea gorgonian octocorals represent valuable archives of past oceanic climate change. Similar to the rings of trees, deep-sea gorgonian octocorals form their skeletons in distinct growth increments, and the chemical composition of these growth bands record changes in their environment over time. The ratios of carbon and nitrogen stable isotopes in the sinking particulate organic matter (POM) that the corals feed upon drive the δ13C and δ15N of the organic material in their growth bands. Changes in the coral skeletal δ13C and δ15N therefore reflect changes in surface water nutrient levels and primary productivity. Here, we measured δ13C and δ15N across the growth bands of three Acanthogorgia sp. and two Eugoria rubens specimens collected from the Channel Islands National Marine Sanctuary in California in 2015 to study inter- and intraspecies variability and develop these species as archives of surface water processes. The taxa represent two different depth strata in the Southern California Bight; Acanthogorgia are typically observed 150-400 meters deep, while Eugorgia corals occur in relatively shallower waters between 50-100 meters deep. Results will be interpreted in the context of eastern Pacific POM values and local environmental influences to examine changes in the corals' food source. Results will also provide information on subsequent alteration of carbon and nitrogen after their incorporation into Acanthogorgia and Eugoria skeletons to aid future study of these corals as proxy records of oceanic climate change.

Diet-to-female and female-to-pup isotopic discrimination in South American sea lions.

PubMed

Drago, Massimiliano; Franco-Trecu, Valentina; Cardona, Luis; Inchausti, Pablo

2015-08-30

The use of accurate, species-specific diet-tissue discrimination factors is a critical requirement when applying stable isotope mixing models to predict consumer diet composition. Thus, diet-to-female and female-to-pup isotopic discrimination factors in several tissues for both captive and wild South American sea lions were estimated to provide appropriate values for quantifying feeding preferences at different timescales in the wild populations of this species. Stable carbon and nitrogen isotope ratios in the blood components of two female-pup pairs and females' prey muscle from captive individuals were determined by elemental analyzer/isotope ratio mass spectrometry (EA/IRMS) to calculate the respective isotopic discrimination factors. The same analysis was carried out in both blood components, and skin and hair tissues for eight female-pup pairs from wild individuals. Mean diet-to-female Δ(13) C and Δ(15) N values were higher than the female-to-pup ones. Pup tissues were more (15) N-enriched than their mothers but (13) C-depleted in serum and plasma tissues. In most of the tissue comparisons, we found differences in both Δ(15) N and Δ(13) C values, supporting tissue-specific discrimination. We found no differences between captive and wild female-to-pup discrimination factors either in Δ(13) C or Δ(15) N values of blood components. Only the stable isotope ratios in pup blood are good proxies of the individual lactating females. Thus, we suggest that blood components are more appropriate to quantify the feeding habits of wild individuals of this species. Furthermore, because female-to-pup discrimination factors for blood components did not differ between captive and wild individuals, we suggest that results for captive experiments can be extrapolated to wild South American sea lion populations. Copyright © 2015 John Wiley & Sons, Ltd.

Patterns in Stable Isotope Values of Nitrogen and Carbon in ...

EPA Pesticide Factsheets

Stable isotope measurements of nitrogen and carbon (15N, 13ddC) are often used to characterize estuarine, nearshore, and open ocean ecosystems. Reliable information about the spatial distribution of base-level stable isotope values, often represented by primary producers, is critical to interpreting values in these ecosystems. While base-level isotope data are generally readily available for estuaries, nearshore coastal waters, and the open ocean, the continental shelf is less studied. To address this, and as a first step toward developing a surrogate for base-level isotopic signature in this region, we collected surface and deep water samples from the United States’ eastern continental shelf in the Western Atlantic Ocean, from the Gulf of Maine to Cape Hatteras, periodically between 2000 and 2013. During the study, particulate matter 15dN values ranged from 0.8 to 17.4‰, and 13dC values from −26.4 to −15.6‰over the region. We used spatial autocorrelation analysis and random forest modeling to examine the spatial trends and potential environmental drivers of the stable isotope values. We observed general trends toward lower values for both nitrogen and carbon isotopes at the seaward edge of the shelf. Conversely, higher 15dN and 13dC values were observed on the landward edge of the shelf, in particular in the southern portion of the sampling area. Across all sites, the magnitude of the difference between the 15dN of subsurface and surface particulate m

The graphene phonon dispersion with C12 and C13 isotopes

NASA Astrophysics Data System (ADS)

Whiteway, Eric; Bernard, Simon; Yu, Victor; Austing, D. Guy; Hilke, Michael

2013-12-01

Using very uniform large scale chemical vapor deposition grown graphene transferred onto silicon, we were able to identify 15 distinct Raman lines associated with graphene monolayers. This was possible thanks to a combination of different carbon isotopes and different Raman laser energies and extensive averaging without increasing the laser power. This allowed us to obtain a detailed experimental phonon dispersion relation for many points in the Brillouin zone. We further identified a D+D' peak corresponding to a double phonon process involving both an inter- and intra-valley phonon. In order to both eliminate substrate effects and to probe large areas, we undertook to study Raman scattering for large scale chemical vapor deposition (CVD) grown graphene using two different isotopes (C12 and C13) so that we can effectively exclude and subtract the substrate contributions, since a heavier mass downshifts only the vibrational properties, while keeping all other properties the same.

Substitution and protonation effects on spin-spin coupling constants in prototypical aromatic rings: C6H6, C5H5N and C5H5P.

PubMed

Del Bene, Janet E; Elguero, José

2006-08-01

Ab initio equation-of-motion coupled cluster calculations have been carried out to evaluate one-, two-, and three-bond 13C-13C, 15N-13C, 31P-13C coupling constants in benzene, pyridine, pyridinium, phosphinine, and phosphininium. The introduction of N or P heteroatoms into the aromatic ring not only changes the magnitudes of the corresponding X-C coupling constants (J, for X = C, N, or P) but also the signs and magnitudes of corresponding reduced coupling constants (K). Protonation of the heteroatoms also produces dramatic changes in coupling constants and, by removing the lone pair of electrons from the sigma-electron framework, leads to the same signs for corresponding reduced coupling constants for benzene, pyridinium, and phosphininium. C-C coupling constants are rather insensitive to the presence of the heteroatoms and protonation. All terms that contribute to the total coupling constant (except for the diamagnetic spin-orbit (DSO) term) must be computed if good agreement with experimental data is to be obtained. Copyright 2006 John Wiley & Sons, Ltd.

POLARIZATION OF NEUTRONS BY THE STRIPPING REACTION C$sup 12$(d,n)N$sup 1$$sup 3$ (in French)

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

Budzanowski, A.; Grotowski, K.; Niewodniczanski, H.

1960-05-01

The polarization of neutrcns emitted from the stripping reaction C/sup 12/(d,n)N/sup 13/ hns been investigated at the reaction angle was / sub lab/ = 15 tained and deuteron energy E/sub d/ = 12.9 Mev. The polarization of neutrons connected with the 3.56 Mev energy level in N/sup 13/ nucleus was found to be --(0.39 combination rat 0.11). Also some general remarks concerning the preliminary results of the polarization of neutrons at the reaction angles 30 tained , 45 tained , and 60 tained are given. (auth)

Influence of dietary carbon on mercury bioaccumulation in streams of the Adirondack Mountains of New York and the Coastal Plain of South Carolina, USA

USGS Publications Warehouse

Riva-Murray, Karen; Bradley, Paul M.; Chasar, Lia C.; Button, Daniel T.; Brigham, Mark E.; Eikenberry, Barbara C. Scudder; Journey, Celeste A.; Lutz, Michelle A.

2013-01-01

We studied lower food webs in streams of two mercury-sensitive regions to determine whether variations in consumer foraging strategy and resultant dietary carbon signatures accounted for observed within-site and among-site variations in consumer mercury concentration. We collected macroinvertebrates (primary consumers and predators) and selected forage fishes from three sites in the Adirondack Mountains of New York, and three sites in the Coastal Plain of South Carolina, for analysis of mercury (Hg) and stable isotopes of carbon (δ13C) and nitrogen (δ15N). Among primary consumers, scrapers and filterers had higher MeHg and more depleted δ13C than shredders from the same site. Variation in δ13C accounted for up to 34 % of within-site variation in MeHg among primary consumers, beyond that explained by δ15N, an indicator of trophic position. Consumer δ13C accounted for 10 % of the variation in Hg among predatory macroinvertebrates and forage fishes across these six sites, after accounting for environmental aqueous methylmercury (MeHg, 5 % of variation) and base-N adjusted consumer trophic position (Δδ15N, 22 % of variation). The δ13C spatial pattern within consumer taxa groups corresponded to differences in benthic habitat shading among sites. Consumers from relatively more-shaded sites had more enriched δ13C that was more similar to typical detrital δ13C, while those from the relatively more-open sites had more depleted δ13C. Although we could not clearly attribute these differences strictly to differences in assimilation of carbon from terrestrial or in-channel sources, greater potential for benthic primary production at more open sites might play a role. We found significant variation among consumers within and among sites in carbon source; this may be related to within-site differences in diet and foraging habitat, and to among-site differences in environmental conditions that influence primary production. These observations suggest that different foraging strategies and habitats influence MeHg bioaccumulation in streams, even at relatively small spatial scales. Such influence must be considered when selecting lower trophic level consumers as sentinels of MeHg bioaccumulation for comparison within and among sites.

13C AND 15N IN MICROARTHROPODS REVEAL LITTLE RESPONSE OF DOUGLAS-FIR ECOSYSTEMS TO CLIMATE CHANGE

EPA Science Inventory

Understanding ecosystem carbon (C) and nitrogen (N) cycling under global change requires experiments maintaining natural interactions among soil structure, soil communities, nutrient availability, and plant growth. In model Douglas-fir ecosystems maintained for five growing seaso...

Effect on a long-term afforestation of pine in a beech domain in NE-Spain as reflected in soil C and N isotopic signature

NASA Astrophysics Data System (ADS)

Girona García, Antonio; Badía-Villas, David; González-Pérez, José Antonio; Tomás Jiménez-Morillo, Nicasio; Martí-Dalmau, Clara

2015-04-01

The replacement of native beech forests (Fagus sylvatica) by Scots pine (Pinus sylvestris) afforestation may exert changes in soil properties, particularly in soil organic matter (SOM) (Carceller and Vallejo, 1996). Stable isotopic signatures of light elements (d13C, d15N) in soils and plants are valuable proxies for the identification of biogeochemical processes and their rates in the pedosphere (Andreeva et al., 2013 and refs therein). In this work the C and N stable isotopic analysis is used as a proxy to detect changes in SOM surrogated to the effect of centennial replacement of beech by the Scots pinewood. Two acid soil profiles, developed on quartzites under a humid climate at an altitude of 1400-1500 masl, have been sampled in Moncayo (Iberian range, NE-Spain). For each soil profile three O-layers (litter: OL, fragmented litter OF and humified litter OH) and mineral soil horizons (Ah, E, Bhs and C) were sampled. Content and bulk isotopic signature of light elements (C and N) were analysed in a Flash 2000 elemental micro-analyser coupled via a ConFlo IV interface to a Delta V Advantage isotope ratio mass spectrometer (IRMS) (Thermo Scientific, Bremen, Germany). Isotopic ratios are reported as parts per thousand deviations from appropriate standards. The standard deviations of d13C and d15N were typically less than ± 0.05 per thousand, ± 0.2 per thousand, respectively. After 100 years since the pine afforestation, no differences on C content were observed in the O-layers, ranging from 30-47% in pine soils and 37-47 % in beech soils. Similarly, no differences on N content were observed in the O-layers, ranging from 1.24-1.86 % in pine soils and 1.70-1.71 % in beech soils. C and N contents decrease progressively in depth with the exception of E-horizons where the lowest C and N content values were found. C/N ratio is higher in pine soil (20.7-38.1) than in beech O soil horizons (21.8-27.5), showing similar behavior with soil depth. Pine biomass was slightly enriched in 13C as compared to that from beech (OL enrichment factor= 1.24 ± 0.13 per thousand). Along the soil profile the C isotopic signature (d13C) reflects the main vegetation signature being higher in pine than beech in the organic soil horizons (OL, OF and OH) down to the first mineral Ah horizon. At deeper horizons d13C value tends to equal that of the original beech soil indicating a limited influence of the afforested specie with depth even 100 years after afforestation. A consistent enrichment in d15N with depth was observed in the two profiles. This N enrichments have been related with progressive N losses being particularly pronounced in forest soils (Szpak, 2014 and refs therein). This phenomenon can be also related to migrations of N forms in a more evolved organic matter. In this view N losses in organic layers under beech seem to be less pronounced that under the alien pine. REFERENCES: Andreeva BD, Zech M, Glaser B, Erbajeva MA, Chimitdorgieva, Ermakova OD, Zech, W. (2013). Stable isotope (δ13C, δ15N, δ18O) record of soils in Buryatia, southern Siberia: Implications for biogeochemical and paleoclimatic interpretations. Quaternary International 290-291 (2013) 82-94 pp. Carceller F, Vallejo VR (1996). Influencia de la vegetación en los procesos de podsolización en los suelos de la Sierra del Moncayo (Zaragoza). Geogaceta 1127-1130. Szpak P (2014). Complexities of nitrogen isotope biogeochemistry in plant-soil systems: implications for the study of ancient agricultural and animal management practices. Front. Plant Sci. 5: 288 1-19 pp. Acknowledgements: This study is part of the results of the FUEGOSOL (CGL2013-43440-R) and GEOFIRE Projects (CGL2012-38655-C04-01) funded by the Spanish Ministry for Economy and Competitiveness. N.T Jiménez-Morillo is funded by a FPI research grant (BES-2013-062573).

Isotopic incorporation and the effects of fasting and dietary lipid content on isotopic discrimination in large carnivorous mammals

USGS Publications Warehouse

Rode, Karyn D.; Stricker, Craig A.; Erlenbach, Joy; Robbins, Charles T.; Cherry, Seth; Newsome, Seth D.; Cutting, Amy; Jensen, Shannon; Stenhouse, Gordon; Brooks, Matt; Hash, Amy; Nicassio, Nicole

2016-01-01

There has been considerable emphasis on understanding isotopic discrimination for diet estimation in omnivores. However, discrimination may differ for carnivores, particularly species that consume lipid-rich diets. Here, we examined the potential implications of several factors when using stable isotopes to estimate the diets of bears, which can consume lipid-rich diets and, alternatively, fast for weeks to months. We conducted feeding trials with captive brown bears (Ursus arctos) and polar bears (Ursus maritimus). As dietary lipid content increased to ∼90%, we observed increasing differences between blood plasma and diets that had not been lipid extracted (∆13Ctissue-bulk diet) and slightly decreasing differences between plasma δ13C and lipid-extracted diet. Plasma Δ15Ntissue-bulk diet increased with increasing protein content for the four polar bears in this study and data for other mammals from previous studies that were fed purely carnivorous diets. Four adult and four yearling brown bears that fasted 120 d had plasma δ15N values that changed by <±2‰. Fasting bears exhibited no trend in plasma δ13C. Isotopic incorporation in red blood cells and whole blood was ≥6 mo in subadult and adult bears, which is considerably longer than previously measured in younger and smaller black bears (Ursus americanus). Our results suggest that short-term fasting in carnivores has minimal effects on δ13C and δ15N discrimination between predators and their prey but that dietary lipid content is an important factor directly affecting δ13C discrimination and indirectly affecting δ15N discrimination via the inverse relationship with dietary protein content.

Stable C and N isotopic composition of cold-water corals from the Newfoundland and Labrador continental slope: Examination of trophic, depth and spatial effects

NASA Astrophysics Data System (ADS)

Sherwood, Owen A.; Jamieson, Robyn E.; Edinger, Evan N.; Wareham, Vonda E.

2008-10-01

With the aim of understanding of the trophic ecology of cold-water corals, this paper explores the tissue δ13C and δ15N values of 11 'coral' species (8 alcyonacean, 1 antipatharian, 1 pennatulacean, 1 scleractinian) collected along the Newfoundland and Labrador continental slope. Isotopic results delimit species along continua of trophic level and food lability. With an isotopic signature similar to macrozooplankton, Paragorgia arborea occupies the lowest trophic level and most likely feeds on fresh phytodetritus. Primnoa resedaeformis occupies a slightly higher trophic level, likely supplementing its diet with microzooplankton. Bathypathes arctica, Pennatulacea and other alcyonaceans ( Acanella arbuscula, Acanthogorgia armata, Anthomastus grandiflorus, Duva florida, Keratoisis ornata, Paramuricea sp.) had higher δ13C and δ15N values, suggesting these species feed at higher trophic levels and on a greater proportion of more degraded POM. Flabellum alabastrum had an isotopic signature similar to that of snow crab, indicating a primarily carnivorous diet. Isotopic composition did not vary significantly over a depth gradient of 50-1400 m. Coral δ13C increased slightly (<1‰) from the Hudson Strait to the southern Grand Banks, but δ15N did not. By modulating the availability and quality of suspended foods, substrate likely exerts a primary influence on the feeding habits of cold-water corals.

Salmon-derived nitrogen in terrestrial invertebrates from coniferous forests of the Pacific Northwest

PubMed Central

2002-01-01

Background Bi-directional flow of nutrients between marine and terrestrial ecosystems can provide essential resources that structure communities in transitional habitats. On the Pacific coast of North America, anadromous salmon (Oncorhynchus spp.) constitute a dominant nutrient subsidy to aquatic habitats and riparian vegetation, although the contribution to terrestrial habitats is not well established. We use a dual isotope approach of δ15N and δ13C to test for the contribution of salmon nutrients to multiple trophic levels of litter-based terrestrial invertebrates below and above waterfalls that act as a barrier to salmon migration on two watersheds in coastal British Columbia. Results Invertebrates varied predictably in δ15N with enrichment of 3–8‰ below the falls compared with above the falls in all trophic groups on both watersheds. We observed increasing δ15N levels in our invertebrate groups with increasing consumption of dietary protein. Invertebrates varied in δ13C but did not always vary predictably with trophic level or habitat. From 19.4 to 71.5% of invertebrate total nitrogen was originally derived from salmon depending on taxa, watershed, and degree of fractionation from the source. Conclusions Enrichment of δ15N in the invertebrate community below the falls in conjunction with the absence of δ13C enrichment suggests that enrichment in δ15N occurs primarily through salmon-derived nitrogen subsidies to litter, soil and vegetation N pools rather than from direct consumption of salmon tissue or salmon tissue consumers. Salmon nutrient subsidies to terrestrial habitats may result in shifts in invertebrate community structure, with subsequent implications for higher vertebrate consumers, particularly the passerines. PMID:11914157

Perceptual responses while wearing an American football uniform in the heat.

PubMed

Johnson, Evan C; Ganio, Matthew S; Lee, Elaine C; Lopez, Rebecca M; McDermott, Brendon P; Casa, Douglas J; Maresh, Carl M; Armstrong, Lawrence E

2010-01-01

The protective equipment worn during American football has been shown to increase thermal strain; however, the perception of this increased heat has not been examined. To evaluate perceptual responses of American football players while wearing different uniforms during exercise in the heat and to evaluate how these responses may be used to monitor athlete safety. Randomized controlled trial. Human Performance Laboratory. Ten men with more than 3 years of competitive experience as football linemen (age = 23.8 +/- 1.3 years, height = 183.9 +/- 1.8 cm, mass = 117.4 +/- 3.5 kg, body fat = 30.1% +/- 1.7%) participated. On 3 occasions in hot, humid (33 degrees C, 48%-49% relative humidity) environmental conditions, participants completed 10 minutes of strenuous repetitive box lifting (RBL), 10 minutes of seated rest, and up to 60 minutes of treadmill walking. At each trial, they wore a different uniform condition: control (CON) clothing comprising shorts, socks, and sneakers; partial (PART) National Football League (NFL) uniform comprising the uniform without helmet or shoulder pads; or full (FULL) NFL uniform. Exercise, meals, and hydration status were controlled. Rectal temperature (T(re)), skin temperature (T(sk)), rating of perceived exertion (RPE), thermal perception (THM), perception of thirst (TST), and perception of muscle pain (MPN) were obtained for time points matched across trials. Nineteen of the 30 trials ended before 60 minutes of treadmill walking as a result of participant exhaustion. Mean treadmill time was longer for the CON condition (51.7 +/- 13.4 minutes) than for the PART (43.1 +/- 15.6 minutes; t(9) = 3.092, P = .01) or the FULL (36.2 +/- 13.2 minutes; t(9) = 4.393, P = .002) conditions. Neck and forearm T(sk) increased between the initial time point and the end of exercise in the PART (33.6 +/- 0.9 degrees C and 35.0 +/- 0.6 degrees C, respectively; F(2,18) = 9.034, P < .001) and the FULL (33.4 +/- 0.9 degrees C and 35.2 +/- 0.6 degrees C, respectively; F(2,18) = 21.011, P = .002) conditions. Rate of T(re) rise was greater in the FULL (0.042 +/- 0.010 degrees C/min) than in the PART (0.034 +/- 0.006 degrees C/min) condition (F(2,27) = 10.69, P = .04). We found a relationship at the post-RBL and final time points between RPE and THM (r = 0.75, P < .001 and r = 0.59, P < .001, respectively), RPE and TST (r = 0.76, P < .001 and r = 0.61, P < .001, respectively), and RPE and MPN (r = 0.63, P < .001 and r = 0.64, P < .001, respectively). The RPE was greater at the end of exercise in the PART (17 +/- 2) and FULL (18 +/- 1) conditions than in the CON (15 +/- 3) condition (F(2,18) = 7.403, P = .005). Although no differences in perceptual scales existed between the PART and FULL conditions, the T(sk) and rate of T(re) increase differed, indicating that football athletes find it difficult to perceptually rate exercise conditions as potentially dangerous hyperthermia develops. In addition, correlations between the perceptual scales further defined perceptual responses during exercise in the heat.

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

Intensity correction for multichannel hyperpolarized 13C imaging of the heart.

PubMed

Dominguez-Viqueira, William; Geraghty, Benjamin J; Lau, Justin Y C; Robb, Fraser J; Chen, Albert P; Cunningham, Charles H

2016-02-01

Develop and test an analytic correction method to correct the signal intensity variation caused by the inhomogeneous reception profile of an eight-channel phased array for hyperpolarized (13) C imaging. Fiducial markers visible in anatomical images were attached to the individual coils to provide three dimensional localization of the receive hardware with respect to the image frame of reference. The coil locations and dimensions were used to numerically model the reception profile using the Biot-Savart Law. The accuracy of the coil sensitivity estimation was validated with images derived from a homogenous (13) C phantom. Numerical coil sensitivity estimates were used to perform intensity correction of in vivo hyperpolarized (13) C cardiac images in pigs. In comparison to the conventional sum-of-squares reconstruction, improved signal uniformity was observed in the corrected images. The analytical intensity correction scheme was shown to improve the uniformity of multichannel image reconstruction in hyperpolarized [1-(13) C]pyruvate and (13) C-bicarbonate cardiac MRI. The method is independent of the pulse sequence used for (13) C data acquisition, simple to implement and does not require additional scan time, making it an attractive technique for multichannel hyperpolarized (13) C MRI. © 2015 Wiley Periodicals, Inc.

Simulated Air Launch Environment. Volume 1

DTIC Science & Technology

1974-10-01

area. The same is true at the aft end where the large steel fairing provides a considerable heat sink. One would, of course, expect similar gradients...111 SZ-110 TZ-51 C0-17 C2-15 C2-16":, T2-17 T2- 15 TZ- 16:’" TZ-1 TZ-2 T2-3 TZ-4 TZ-5 IM H13 N3-44 N3-43 N3-45 T3-44 T3-43 T3-108 S3-104 N3-47 C3-20...Of course, routing of the lead wires must bbe compatible with tooling . 0 The GFE gages used in this program were of poor quality which compromised the

Molecular and polymeric uranyl and thorium hybrid materials featuring methyl substituted pyrazole dicarboxylates and heterocyclic 1,3-diketones

NASA Astrophysics Data System (ADS)

Carter, Korey P.; Kerr, Andrew T.; Taydakov, Ilya V.; Cahill, Christopher L.

2018-02-01

A series of seven novel f-element bearing hybrid materials have been prepared from either methyl substituted 3,4 and 4,5-pyrazoledicarboxylic acids, or heterocyclic 1,3- diketonate ligands using hydrothermal conditions. Compounds 1, [UO2(C6H4N2O4)2(H2O)], and 3, [Th(C6H4N2O4)4(H2O)5]·H2O feature 1-Methyl-1H-pyrazole-3,4-dicarboxylate ligands (SVI-COOH 3,4), whereas 2, [UO2(C6H4N2O4)2(H2O)], and 4, [Th(C6H5N2O4)(OH)(H2O)6]2·2(C6H5N2O4)·3H2O feature 1-Methyl-1H-pyrazole-4,5-dicarboxylate moieties (SVI-COOH 4,5). Compounds 5, [UO2(C13H15N4O2)2(H2O)]·2H2O and 6, [UO2(C11H11N4O2)2(H2O)]·4.5H2O feature 1,3-bis(4-N1-methyl-pyrazolyl)propane-1,3-dione and 1,3-bis(4-N1,3-dimethyl-pyrazolyl)propane-1,3-dione respectively, whereas the heterometallic 7, [UO2(C11H11N4O2)2(CuCl2)(H2O)]·2H2O is formed by using 6 as a metalloligand starting material. Single crystal X-ray diffraction indicates that all coordination to either [UO2]2+ or Th(IV) metal centers is through O-donation as anticipated. Room temperature, solid-state luminescence studies indicate characteristic uranyl emissive behavior for 1 and 2, whereas those for 5 and 6 are weak and poorly resolved.

Isotopic analysis of Bothrops atrox in Amazonian forest

NASA Astrophysics Data System (ADS)

Martinez, M. G.; Silva, A. M.; Chalkidis, H.; de Oliveira Júnior, R. C.; Camargo, P. B.

2012-12-01

The poisoning of snakes is considered a public health problem, especially in populations from rural areas of tropical and subtropical countries. In Brazil, the 26,000 snakebites, 90% are of the genus Bothrops, and Bothrops atrox species predominant in the Amazon region including all the Brazilian Amazon. Research shows that using stable isotopes, we can verify the isotopic composition of tissues of animals that depend mainly on food, water ingested and inhaled gases. For this study, samples taken from Bothrops atrox (B. atrox), in forest using pitfall traps and fall ("Pitt-fall traps with drift fence"). The analyzes were performed by mass spectrometry, where the analytical error is 0.3‰ for carbon and 0.5‰ to nitrogen. The results of the forest animals are significantly different from results of animal vivarium. The average values of the tissues and venoms of snakes of the forest for carbon-13 and nitrogen-15 are: δ13C = -24.68‰ and δ15N = 14.22‰ and mean values of tissue and poisons snakes vivarium (Instituto Butantan) to carbon-13 and nitrogen-15 are δ13C = -20.47‰ and δ15N = 8.36‰, with a significantly different due to different sources of food animals. Based on all results isotopic δ13C and δ15N, we can suggest that changes as the power of the serpent, (nature and captivity), changes occur in relation to diet and environment as the means of the isotopic data are quite distinct, showing that these changes can also cause metabolic changes in the body of the animal itself and the different periods of turnover of each tissue analyzed.

2-Acetyl-1,1,3,3-tetra­methyl­guanidine

PubMed Central

Tiritiris, Ioannis

2012-01-01

In the mol­ecule of the title compound, C7H15N3O, the central C atom is surrounded in a nearly ideal trigonal–planar geometry by three N atoms. The C—N bond lengths in the CN3 unit are 1.3353 (13), 1.3463 (12) and 1.3541 (13) Å, indicating an inter­mediate character between a single and a double bond for each C—N bond. The bonds between the N atoms and the terminal C-methyl groups all have values close to that of a typical single bond [1.4526 (13)–1.4614 (14) Å]. In the crystal, the guanidine mol­ecules are connected by weak C—H⋯O and C—H⋯N hydrogen bonds, generating layers parallel to the ab plane. PMID:23125768

Combining Nuclear Magnetic Resonance Spectroscopy and Density Functional Theory Calculations to Characterize Carvedilol Polymorphs.

PubMed

Rezende, Carlos A; San Gil, Rosane A S; Borré, Leandro B; Pires, José Ricardo; Vaiss, Viviane S; Resende, Jackson A L C; Leitão, Alexandre A; De Alencastro, Ricardo B; Leal, Katia Z

2016-09-01

The experiments of carvedilol form II, form III, and hydrate by (13)C and (15)N cross-polarization magic-angle spinning (CP MAS) are reported. The GIPAW (gauge-including projector-augmented wave) method from DFT (density functional theory) calculations was used to simulate (13)C and (15)N chemical shifts. A very good agreement was found for the comparison between the global results of experimental and calculated nuclear magnetic resonance (NMR) chemical shifts for carvedilol polymorphs. This work aims a comprehensive understanding of carvedilol crystalline forms employing solution and solid-state NMR as well as DFT calculations. Copyright © 2016. Published by Elsevier Inc.

Carbon and nitrogen stable isotopes in fast food: Signatures of corn and confinement

PubMed Central

Jahren, A. Hope; Kraft, Rebecca A.

2008-01-01

Americans spend >100 billion dollars on restaurant fast food each year; fast food meals comprise a disproportionate amount of both meat and calories within the U.S. diet. We used carbon and nitrogen stable isotopes to infer the source of feed to meat animals, the source of fat within fries, and the extent of fertilization and confinement inherent to production. We sampled food from McDonald's, Burger King, and Wendy's chains, purchasing >480 servings of hamburgers, chicken sandwiches and fries within geographically distributed U.S. cities: Los Angeles, San Francisco, Denver, Detroit, Boston, and Baltimore. From the entire sample set of beef and chicken, only 12 servings of beef had δ13C < −21‰; for these animals only was a food source other than corn possible. We observed remarkably invariant values of δ15N in both beef and chicken, reflecting uniform confinement and exposure to heavily fertilized feed for all animals. The δ13C value of fries differed significantly among restaurants indicating that the chains used different protocols for deep-frying: Wendy's clearly used only corn oil, whereas McDonald's and Burger King favored other vegetable oils; this differed from ingredient reports. Our results highlighted the overwhelming importance of corn agriculture within virtually every aspect of fast food manufacture. PMID:19001276

Recoupling of Heteronuclear Dipolar Interactions with Rotational-Echo Double-Resonance at High Magic-Angle Spinning Frequencies

NASA Astrophysics Data System (ADS)

Jaroniec, Christopher P.; Tounge, Brett A.; Rienstra, Chad M.; Herzfeld, Judith; Griffin, Robert G.

2000-09-01

Heteronuclear dipolar recoupling with rotational-echo double-resonance (REDOR) is investigated in the rapid magic-angle spinning regime, where radiofrequency irradiation occupies a significant fraction of the rotor period (10-60%). We demonstrate, in two model 13C-15N spin systems, [1-13C, 15N] and [2-13C, 15N]glycine, that REDOR ΔS/S0 curves acquired at high MAS rates and relatively low recoupling fields are nearly identical to the ΔS/S0 curve expected for REDOR with ideal δ-function pulses. The only noticeable effect of the finite π pulse length on the recoupling is a minor scaling of the dipolar oscillation frequency. Experimental results are explained using both numerical calculations and average Hamiltonian theory, which is used to derive analytical expressions for evolution under REDOR recoupling sequences with different π pulse phasing schemes. For xy-4 and extensions thereof, finite pulses scale only the dipolar oscillation frequency by a well-defined factor. For other phasing schemes (e.g., xx-4 and xx¯-4) both the frequency and amplitude of the oscillation are expected to change.

Multi-Spectroscopic Analysis of Seed Quality and 13C-Stable-Iotopologue Monitoring in Initial Growth Metabolism of Jatropha curcas L.

PubMed Central

Komatsu, Takanori; Ohishi, Risa; Shino, Amiu; Akashi, Kinya; Kikuchi, Jun

2014-01-01

In the present study, we applied nuclear magnetic resonance (NMR), as well as near-infrared (NIR) spectroscopy, to Jatropha curcas to fulfill two objectives: (1) to qualitatively examine the seeds stored at different conditions, and (2) to monitor the metabolism of J. curcas during its initial growth stage under stable-isotope-labeling condition (until 15 days after seeding). NIR spectra could non-invasively distinguish differences in storage conditions. NMR metabolic analysis of water-soluble metabolites identified sucrose and raffinose family oligosaccharides as positive markers and gluconic acid as a negative marker of seed germination. Isotopic labeling patteren of metabolites in germinated seedlings cultured in agar-plate containg 13C-glucose and 15N-nitrate was analyzed by zero-quantum-filtered-total correlation spectroscopy (ZQF-TOCSY) and 13C-detected 1H-13C heteronuclear correlation spectroscopy (HETCOR). 13C-detected HETOCR with 13C-optimized cryogenic probe provided high-resolution 13C-NMR spectra of each metabolite in molecular crowd. The 13C-13C/12C bondmer estimated from 1H-13C HETCOR spectra indicated that glutamine and arginine were the major organic compounds for nitrogen and carbon transfer from roots to leaves. PMID:25401292

Forazoline A: Marine-derived polyketide with antifungal in vivo efficacy

DOE PAGES

Wyche, Thomas P.; Piotrowski, Jeff S.; Hou, Yanpeng; ...

2014-09-04

Forazoline A, a novel antifungal polyketide with in vivo efficacy against Candida albicans, was discovered using LCMS-based metabolomics to investigate marine-invertebrate-associated bacteria. Forazoline A had a highly unusual and unprecedented skeleton. Acquisition of 13C– 13C gCOSY and 13C– 15N HMQC NMR data provided the direct carbon–carbon and carbon–nitrogen connectivity, respectively. This approach represents the first example of determining direct 13C– 15N connectivity for a natural product. In this paper, using yeast chemical genomics, we propose that forazoline A operated through a new mechanism of action with a phenotypic outcome of disrupting membrane integrity.

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

NASA Astrophysics Data System (ADS)

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

2015-11-01

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

A universal sample manipulator with 50 kV negative bias

NASA Astrophysics Data System (ADS)

Kenny, M. J.; Wielunski, L. S.; Scott, M. D.; Clissold, R. A.; Stevenson, D.; Baxter, G.

1991-04-01

A manipulator incorporating a number of novel features has been built for a research ion implanter. The system is designed to enable uniform dose implantation of both planar and nonplanar surfaces by incorporating one translational and two rotational degrees of freedom. Negative target bias of up to 50 kV may be applied to the target, thus increasing the ion energy by this amount. The target chamber and all external manipulator controls are grounded. With the exception of the high voltage power supply, cable and feedthrough, all high voltage components are within the vacuum system. A secondary electron suppression cage which can be held at a negative bias of up to 60 kV relative to the chamber (i.e. 10 kV relative to the manipulator) surrounds the manipulator. Performance has been evaluated using 15N ions and nuclear reaction analysis through 15N(p,α) 12C to profile ion concentrations for dose uniformity and for ion depth at elevated target potentials.

Paleoreconstruction of organic carbon inputs to an oxbow lake in the Mississippi River watershed: Effects of dam construction and land use change on regional inputs

NASA Astrophysics Data System (ADS)

Bianchi, Thomas S.; Galy, Valier; Rosenheim, Brad E.; Shields, Michael; Cui, Xingqian; Van Metre, Peter

2015-10-01

We use a dated sediment core from Lake Whittington (USA) in the lower Mississippi River to reconstruct linkages in the carbon cycling and fluvial sediment dynamics over the past 80 years. Organic carbon (OC) sources were characterized using bulk (δ13C, ramped pyrolysis-oxidation (PyrOx) 14C, δ15N, and TN:OC ratios) and compound-specific (lignin phenols and fatty acids, including δ13C and 14C of the fatty acids) analyses. Damming of the Missouri River in the 1950s, other hydrological modifications to the river, and soil conservation measures resulted in reduced net OC export, in spite of increasing OC concentrations. Decreasing δ13C values coincided with increases in δ15N, TN:OC ratios, long-chain fatty acids, and lignin-phenol concentrations, suggesting increased inputs of soil-derived OC dominated by C3 vegetation, mainly resulting from changes in farming practices and crop distribution. However, ramped PyrOx 14C showed no discernible differences downcore in thermochemical stability, indicating a limited impact on soil OC turnover.

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

NASA Astrophysics Data System (ADS)

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

1994-04-01

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

Effects of lipid extraction on stable isotope ratios in avian egg yolk: Is arithmetic correction a reliable alternative?

USGS Publications Warehouse

Oppel, S.; Federer, R.N.; O'Brien, D. M.; Powell, A.N.; Hollmén, Tuula E.

2010-01-01

Many studies of nutrient allocation to egg production in birds use stable isotope ratios of egg yolk to identify the origin of nutrients. Dry egg yolk contains >50% lipids, which are known to be depleted in 13C. Currently, researchers remove lipids from egg yolk using a chemical lipid-extraction procedure before analyzing the isotopic composition of protein in egg yolk. We examined the effects of chemical lipid extraction on ??13C, ??15N, and ??34S of avian egg yolk and explored the utility of an arithmetic lipid correction model to adjust whole yolk ??13C for lipid content. We analyzed the dried yolk of 15 captive Spectacled Eider (Somateriafischeri) and 20 wild King Eider (S. spectabilis) eggs, both as whole yolk and after lipid extraction with a 2:1 chloroform:methanol solution. We found that chemical lipid extraction leads to an increase of (mean ?? SD) 3.3 ?? 1.1% in ??13C, 1.1 ?? 0.5% in ??15N, and 2.3 ?? 1.1% in ??34S. Arithmetic lipid correction provided accurate values for lipid-extracted S13C in captive Spectacled Eiders fed on a homogeneous high-quality diet. However, arithmetic lipid correction was unreliable for wild King Eiders, likely because of their differential incorporation of macronutrients from isotopically distinct environments during migration. For that reason, we caution against applying arithmetic lipid correction to the whole yolk ??13C of migratory birds, because these methods assume that all egg macronutrients are derived from the same dietary sources. ?? 2010 The American Ornithologists' Union.

Isotopic patterns in caps and stipes in sporocarps reveal patterns of organic nitrogen use by ectomycorrhizal fungi

NASA Astrophysics Data System (ADS)

Hobbie, Erik; Ouimette, Andrew; Chen, Janet

2016-04-01

Current ecosystem models use inorganic nitrogen as the currency of nitrogen acquisition by plants. However, many trees may gain access to otherwise unavailable soil resources, such as soil organic nitrogen, through their symbioses with ectomycorrhizal fungi, and this pathway of nitrogen acquisition may therefore be important in understanding plant responses to environmental change. Different functional groups of ectomycorrhizal fungi vary in their ability to enzymatically access protein and other soil resources. Such fungal parameters as hyphal hydrophobicity, the presence of rhizomorphs (long-distance transport structures), and exploration strategies (e.g., short-distance versus long-distance, mat formation) correspond with how fungi interact with and explore the environment, and the proportions of different exploration types present will shift along environmental gradients such as nitrogen availability. Isotopic differences between caps and stipes may provide a means to test for organic nitrogen use, since caps and stipes differ in δ13C and δ15N as a result of variable proportions of protein and other classes of compounds, and protein should differ isotopically among de novo synthesis, litter sources, and soil sources. Here, we propose that (1) isotopic differences between caps and stipes could be related to organic nitrogen uptake and to the δ13C and δ15N values of different pools of soil-derived or de novo-synthesized amino acids; (2) these isotopic differences will reflect greater acquisition of soil-derived organic nitrogen by exploration types of greater enzymatic capabilities to degrade recalcitrant nitrogen forms, specifically long-distance, medium-distance fringe, and medium-distance mat exploration types. To test these hypotheses, we use a dataset of isotopic values, %N, and %C in 208 cap/stipe samples collected from Oregon, western USA. δ13C differences in caps and stipes in a multiple regression model had an adjusted r2 of 0.292 (p < 0.0001), and were explained best by exploration type (45% of explained variance), the interaction of exploration type and %Ncap-stipe (20%), the interaction of exploration type and %Ncap/stipe (22%), %Ccap-stipe (8%), and %Ncap-stipe (5%). δ15N differences between caps and stipes in a multiple regression model had an adjusted r2 of 0.486 (p < 0.0001), and were explained best by exploration type (47% of explained variance), the interaction of exploration type and %Ncap-stipe (26%), the interaction of exploration type and %Ncap/stipe (14%), %Ncap/stipe (11%),and %Ccap-stipe (2%). We argue that these differences in the 13C and 15N enrichment of caps relative to stipes reflect not only shifts in the proportions of protein and carbohydrates, but also differences in the extent of fluxes and the δ13C and δ15N signatures of soil- and litter-derived organic nitrogen taken up by these fungi. We also propose equations to quantify this uptake. Organic nitrogen from litter (lower δ13C and δ15N) may be incorporated by medium-distance mat, short-distance, and contact exploration types of ectomycorrhizal fungi, whereas long-distance and medium-distance fringe exploration types appeared to incorporate deeper soil organic nitrogen.

Coupling Meteorological, Land Surface and Water Temperature Models in the Mississippi River Basin

NASA Astrophysics Data System (ADS)

Tang, C.; Cooter, E. J.

2017-12-01

Water temperature is a significant factor influencing of the stream ecosystem and water management especially under climate change. In this study, we demonstrate a physically based semi-Lagrangian water temperature model (RBM) coupled with the Variable Infiltration Capacity (VIC) hydrology model and Weather Research & Forecasting Model (WRF) in the Mississippi River Basin (MRB). The results of this coupling compare favorably with observed water temperature data at river gages throughout the MRB. Further sensitivity analysis shows that mean water temperatures increase by 1.3°C, 1.5°C, and 1.8°C in northern, central and southern MRB zones, respectively, under a hypothetical uniform air temperature increase of 3°C. If air temperatures increase uniformly by 6°C in this scenario, then water temperatures are projected to increase by 3.3°C, 3.5°C and 4.0°C. Lastly, downscaled air temperatures from a global climate model are used to drive the coupled VIC and RBM model from 2020 to 2099. Average stream temperatures from 2020 to 2099 increase by 1°C to 8°C above 1950 to 2010 average water temperatures, with non-uniform increases along the river. In some portions of the MRB, stream temperatures could increase above survival thresholds for several native fish species, which are critical components of the stream ecosystem. The increased water temperature accelerates harmful algal blooming which results in a larger dead zone in the Gulf of Mexico.

Stable isotope signatures in bulk samples from two soils with contrasting characteristics. What do they tell about ongoing pedogenic processes?

NASA Astrophysics Data System (ADS)

Jiménez-Morillo, Nicasio T.; dos Anjos Leal, Otávio; Knicker, Heike; Pinheiro Dick, Deborah; González-Vila, Francisco J.; González-Pérez, José A.

2014-05-01

Isotopic ratio mass spectrometry (IRMS) has been proven as a promising tool for the monitoring of biogeochemical processes in soil. In this work, stable isotope signatures of light elements δ15N, δ13C, δ18O and δD were determined for two soils with contrasting characteristics in terms of climate, vegetation, land use and management. The studied soils were a Cambisol from a subtropical area (Paraná region, South Brazil) and an Arenosol from a Mediterranean climate (Andalusia, South Spain). A Flash 2000 HT (N, C, S, H and O) elemental analyzer (Thermo Scientific) coupled to a Delta V Advantage IRMS (Thermo Scientific) was used. Isotopic ratios are reported as parts per thousand (o ) deviations from appropriate standards recognized by the international atomic energy agency (IAEA). In a first approach we took advantage of the well-known different δ13C signature between plants using either the C4 or C3 carbon fixation pathway (O'Leary, 1981). The Arenosol (Spain) revealed a δ13C signature which is clearly in the range of C3 plants (-26 to -30 o ). Different plant canopies (tree, shrubs or ferns) caused only slight variations δ13C (STD= 0.98). In contrast, the Cambisol (Brazil) showed less depletion of the heavier carbon isotope corresponding to C4 predominant vegetation. In addition an increase from -19 o in the soil surface (0 - 5 cm) to -16 o in the subsoil (20 - 30 cm) was observed in line with a recent (2 years old) shift of the land use from the predominant C4 grassland to eucalypt (C3) cultivation. Crossplots of δ15N vs. δ18O may provide information about nitrate (NO3-) sources and N cycling (Kendall, 1998). In the Mediterranean Arenosol this signal (δ18O = 30o δ15N = 2o ) was found compatible with a predominant nitrate atmospheric deposition, whereas the signal in the Brazilian Cambisol pointed to the use of a mineral N fertilization with signs of denitrification processes (δ18O = 13o δ15N = 9o ). No conclusive results could be obtained from the δD isotopic signature probably due to overlapping of the δD signals from the organic and the mineral fractions. For a more detailed analysis steps allowing their separation are necessary (Ruppenthal et al. (2013) and references therein). Kendall, C. 1998. Tracing nitrogen sources and cycling in catchments. In Isotopes Tracers in Catchments Hydrology (C. Kendall and J. J. McDonnell, Eds). Elsevier Science B. V., Amsterdam, 519-576. O'Leary, M.H. 1981. Carbon isotope fraction in plants. Phytochemistry 20: 553-567. Ruppenthal, M., Oelmann, Y., Wilcke, W. 2013. Optimized demineralization technique for the measurement of stable isotope ratios of nonexchangeable H in soil organic matter. Environmental Science and Technology 47: 949-957.

Diabetes induced renal urea transport alterations assessed with 3D hyperpolarized 13 C,15 N-Urea.

PubMed

Bertelsen, Lotte B; Nielsen, Per M; Qi, Haiyun; Nørlinger, Thomas S; Zhang, Xiaolu; Stødkilde-Jørgensen, Hans; Laustsen, Christoffer

2017-04-01

In the current study, we investigated hyperpolarized urea as a possible imaging biomarker of the renal function by means of the intrarenal osmolality gradient. Hyperpolarized three-dimensional balanced steady state 13 C MRI experiments alongside kidney function parameters and quantitative polymerase chain reaction measurements was performed on two groups of rats, a streptozotocin type 1 diabetic group and a healthy control group. A significant decline in intrarenal steepness of the urea gradient was found after 4 weeks of untreated insulinopenic diabetes in agreement with an increased urea transport transcription. MRI and hyperpolarized [ 13 C, 15 N]urea can monitor the changes in the corticomedullary urea concentration gradients in diabetic and healthy control rats. Magn Reson Med 77:1650-1655, 2017. © 2016 International Society for Magnetic Resonance in Medicine. © 2016 International Society for Magnetic Resonance in Medicine.

Overfishing of small pelagic fishes increases trophic overlap between immature and mature striped dolphins in the Mediterranean Sea.

PubMed

Gómez-Campos, Encarna; Borrell, Assumpció; Cardona, Luis; Forcada, Jaume; Aguilar, Alex

2011-01-01

The interactions among diet, ecology, physiology, and biochemistry affect N and C stable isotope signatures in animal tissues. Here, we examined if ecological segregation among animals in relation to sex and age existed by analyzing the signatures of δ(15)N and δ(13)C in the muscle of Western Mediterranean striped dolphins. Moreover, we used a Bayesian mixing model to study diet composition and investigated potential dietary changes over the last two decades in this population. For this, we compared isotope signatures in samples of stranded dolphins obtained during two epizootic events occurring in 1990 and 2007-2008. Mean δ(13)C values for females and males were not significantly different, but age-related variation indicated δ(13)C enrichment in both sexes, suggesting that females and males most likely fed in the same general areas, increasing their consumption of benthic prey with age. Enrichment of δ(15)N was only observed in females, suggesting a preference for larger or higher trophic level prey than males, which could reflect different nutritional requirements. δ(13)C values showed no temporal variation, although the mean δ(15)N signature decreased from 1990 to 2007-2008, which could indicate a dietary shift in the striped dolphin over the last two decades. The results of SIAR indicated that in 1990, hake and sardine together contributed to 60% on the diet of immature striped dolphins, and close to 90% for mature striped dolphins. Conversely, the diet of both groups in 2007-2008 was more diverse, as hake and sardine contributed to less than 40% of the entire diet. These results suggest a dietary change that was possibly related to changes in food availability, which is consistent with the depletion of sardine stocks by fishing.

A high resolution paleo-record of export production using deep-sea coral stable isotope values from a unique HNLC zone on the California Margin

NASA Astrophysics Data System (ADS)

Wright, Z.

2015-12-01

The Sur Ridge, located ~30 km off the Big Sur coast of central California, represents a unique system within the highly productive California Current ecosystem. Its unique high nutrient, but low chlorophyll characteristics are not fully understood. Time series of bulk stable carbon (δ13C) and stable nitrogen (δ15N) isotopes can help us better understand past changes in nutrient dynamics and phytoplankton community baselines for this region in order to better predict future changes. Deep-sea proteinaceous corals are particularly powerful paleoarchives of past ocean conditions. These organisms serve as "living sediment traps," incorporating the stable isotope values of exported particulate organic material (POM) from the surface into their growth layers. The longevity of bamboo corals (Isidella, up to 400 years) makes them excellent resources for creating high resolution, centennial time series of δ13C and δ15N dynamics. Bamboo corals used in this study were harvested during summer of 2014 from 1220 to 1300 m depths. Two corals were milled in sub-millimeter intervals to generate a 200 year time series at approximately three year temporal resolution. Over the past 200 years, deep-sea coral δ13C values ranged from -15.7 to -19.0‰ and δ15N values ranged from 14.4 to 15.9‰, consistent with earlier data from the CA margin. The δ13C records were characterized by long periods of remarkable stability, contrasted with several large shifts (~1900 and ~1960) in δ13C of approximately 1‰. We hypothesize that these shifts likely reflect changes in plankton composition or production associated with regional climate shifts. The δ15N data were more dynamic, including several large shifts (1940 - 1960), as well as periods of apparent decadal scale oscillation (1825 - 1925 and 1965 - present). These shifts may reflect changes in the source or utilization of nitrogen at the base of the food web. Together, these data give us a first look at baseline stability of biogeochemical systems in this unique region, and will be crucial in connecting potential future system changes in climate and upwelling to possible shifts in nutrient dynamics and phytoplankton species composition. 

Molecular structure and conformation of N-2-[3'-(methoxysalicylideneimino)benzyl]-3″-methoxysalicylideneimine

NASA Astrophysics Data System (ADS)

Dey, D. K.; Dey, S. P.; Elmali, A.; Elerman, Y.

2001-05-01

The Schiff base, N-2-[3'-(methoxysalicylideneimino)benzyl]-3″-methoxysalicylidene-imine, 1,2-C 6H 4[NCHC 6H 3(OMe-3')OH-2']CH 2NCHC 6H 3(OMe-3″)OH-2″, has been prepared by the reaction of 2-amino-1-benzylamine and 3-methoxysalicylaldehyde ( o-vanillin) in ethanol. The molecular structure has been confirmed by single crystal X-ray crystallography. The crystal is in the monoclinic space group P2 1/ n with a=16.179(5), b=6.715(5), c=18.780(6) Å, β=100.56(3)°, Dcalc=1.293 mg cm -3, V=2006(2) Å 3 and R=0.0357 for 3929 independent reflections. The 1H and 13C NMR spectra in CDCl 3 solution indicate the retention of solid state structure in solution. The title compound is not planar. Intramolecular hydrogen bonds occur between O(1) and N(1) [2.614(2) Å] and between O(2) and N(2) [2.585(2) Å] atoms, the hydrogen atom essentially being bonded to the oxygen atom. Minimum energy conformations from AM1 were calculated as a function of five torsion angles θ1 (C6-C7-N1-C8), θ2 (C14-N2-C15-C16), θ3 (C9-C8-N1-C7), θ4 (C13-C14-N2-C15) and θ5 (C10-C9-C8-N1), varied every 5°. The optimized geometry of the crystal structure corresponding to the non-planar conformation is the most stable conformation in all calculations. The results strongly indicate that the minimum energy conformation is primarily determined by non-bonded hydrogen-hydrogen repulsions.

Compensated second-order recoupling: application to third spin assisted recoupling†

PubMed Central

Giffard, Mathilde; Hediger, Sabine; Lewandowski, Józef R.; Bardet, Michel; Simorre, Jean-Pierre; Griffin, Robert G.; De Paëpe, Gaël

2015-01-01

We consider the effect of phase shifts in the context of second-order recoupling techniques in solid-state NMR. Notably we highlight conditions leading to significant improvements for the Third Spin Assisted Recoupling (TSAR) mechanism and demonstrate the benefits of resulting techniques for detecting long-distance transfer in biomolecular systems. The modified pulse sequences of PAR and PAIN-CP, Phase-Shifted Proton Assisted Recoupling (AH-PS-PAR) and Phase-Shifted Proton-Assisted Insensitive Nuclei Cross Polarization (ABH-PS-PAIN-CP), still rely on cross terms between heteronuclear dipolar couplings involving assisting protons that mediate zero-quantum polarization transfer between low-γ nuclei (13C–13C, 15N–15N, 15N–13C polarization transfer). Using Average Hamiltonian Theory we show that phase inversion compensates off-resonance contributions and yields improved polarization transfer as well as substantial broadening of the matching conditions. PS-TSAR greatly improves on the standard TSAR based methods because it alleviates their sensitivity to precise RF settings which significantly enhances robustness of the experiments. We demonstrate these new methods on a 19.6 kDa protein (U–[15N, 13C]-YajG) at high magnetic fields (up to 900 MHz 1H frequency) and fast sample spinning (up to 65 kHz MAS frequency). PMID:22513727

Isotopic evidence of weaning in hunter-gatherers from the late holocene in Lake Salitroso, Patagonia, Argentina.

PubMed

Tessone, Augusto; García Guraieb, Solana; Goñi, Rafael A; Panarello, Héctor O

2015-09-01

The timing and duration of breastfeeding and weaning in past hunter-gatherer populations are discussed based on the results of stable carbon and nitrogen isotope analyses undertaken on a Late Holocene skeletal sample from Lake Salitroso in the Patagonian steppe (Argentina). Research in Lake Salitroso is part of a regional project that studies the relationship between hunter-gatherer societies, their organizational systems and the environmental changes during the last 3,000 years in Patagonia. The sample included 52 individuals: 33 subadults and 19 adults of both sexes. They were recovered from 24 burial stone structures, locally called chenques, with dates ranging from ca. 800 BP to 350 BP. Ribs were selected for collagen extraction and measurement of (13) C/(12) C and (15) N/(14) N ratios. A δ(13) C mean value of -18.7‰ ± 0.5‰ was obtained, with a range between -19.8‰ and -17.1‰ whereas δ(15) N recorded a mean of 11.9‰ ± 1.1‰ with a range between 10.1‰ and 14.8‰. δ(15) N data showed an age-related pattern with particularly marked difference between values for subadults under the age of 4 and older individuals. As opposed to δ(15) N, δ(13) C showed little variation with age. An early incorporation of supplementary solid food between 0.75 and 2 years of age and a late cessation of breastfeeding at about 5-6 years of age were inferred. This suggests that among this Patagonian hunter-gatherer population weaning was a gradual and lengthy process. These results are consistent with the patterns observed in cross-cultural studies and archaeological samples of hunter-gatherer groups. © 2015 Wiley Periodicals, Inc.

DFT calculations in the assignment of solid-state NMR and crystal structure elucidation of a lanthanum(iii) complex with dithiocarbamate and phenanthroline.

PubMed

Gowda, Vasantha; Laitinen, Risto S; Telkki, Ville-Veikko; Larsson, Anna-Carin; Antzutkin, Oleg N; Lantto, Perttu

2016-12-06

The molecular, crystal, and electronic structures as well as spectroscopic properties of a mononuclear heteroleptic lanthanum(iii) complex with diethyldithiocarbamate and 1,10-phenanthroline ligands (3 : 1) were studied by solid-state 13 C and 15 N cross-polarisation (CP) magic-angle-spinning (MAS) NMR, X-ray diffraction (XRD), and first principles density functional theory (DFT) calculations. A substantially different powder XRD pattern and 13 C and 15 N CP-MAS NMR spectra indicated that the title compound is not isostructural to the previously reported analogous rare earth complexes with the space group P2 1 /n. Both 13 C and 15 N CP-MAS NMR revealed the presence of six structurally different dithiocarbamate groups in the asymmetric unit cell, implying a non-centrosymmetric packing arrangement of molecules. This was supported by single-crystal X-ray crystallography showing that the title compound crystallised in the triclinic space group P1[combining macron]. In addition, the crystal structure also revealed that one of the dithiocarbamate ligands has a conformational disorder. NMR chemical shift calculations employing the periodic gauge including projector augmented wave (GIPAW) approach supported the assignment of the experimental 13 C and 15 N NMR spectra. However, the best correspondences were obtained with the structure where the atomic positions in the X-ray unit cell were optimised at the DFT level. The roles of the scalar and spin-orbit relativistic effects on NMR shielding were investigated using the zeroth-order regular approximation (ZORA) method with the outcome that already the scalar relativistic level qualitatively reproduces the experimental chemical shifts. The electronic properties of the complex were evaluated based on the results of the natural bond orbital (NBO) and topology of the electron density analyses. Overall, we apply a multidisciplinary approach acquiring comprehensive information about the solid-state structure and the metal-ligand bonding of the heteroleptic lanthanum complex.

Leaf wax records of late Holocene hydrologic changes on Abaco Island, Northern Bahamas

NASA Astrophysics Data System (ADS)

Tamalavage, A.; Feakins, S. J.; van Hengstum, P. J.; Louchouarn, P.; Fall, P. L.; Albury, N. A.; Donnelly, J. P.

2016-12-01

Previous pollen-based evidence from Abaco Island (Little Bahama Bank, Northern Bahamas) indicates that the terrestrial forest changed in dominance over the last 1500 years from palms to pines, and that this change is potentially driven by climate and/or anthropogenic factors. Geochemical markers (δ13Corg, δ15Norg,, C/N, and lignin phenols) measured from bulk sedimentary matter that has accumulated in Blackwood Sinkhole on Abaco Island also support the pollen-based evidence that vegetation has not been constant throughout the late Holocene (last 3000 years). More specifically, these geochemical markers document three intervals where sedimentary deposition was dominated by a different source of organic matter. These changes are likely driven by the combination of the ecological response to shoreline migration from Holocene sea-level rise, and a southward migration of the Intertropical Convergence Zone (ITCZ) at 1000 Cal yrs BP. However, the specific impact of a southward ITCZ displacement at 1000 Cal yrs BP on Abaco rainfall variability remains uncertain (e.g., quantity, seasonality). This research will explore hydrologic variability associated with regional vegetation changes by measuring precipitation isotopic composition based upon plant leaf wax n-alkanoic acid and n-alkane biomarkers. We find C29 and C31 n-alkanes and C24, C26, C28, and C30 n-alkanoic acids record the same hydrogen isotopic values within uncertainties indicating a uniform terrestrial vegetation source. We find a negative shift (-50‰) towards present in our initial analyses; the results of ongoing work will be presented at the meeting. This multi-proxy approach will allow us to resolve the nature of the leaf wax biomarker hydrogen isotope evidence for past precipitation, including testing for the impacts of vegetation on the hydrological proxy, and testing predictions of a shift in precipitation on Abaco Island over the late Holocene coincident with a southward displacement of the ITCZ.

Stable isotope ratios in freshwater mussel shells as high resolution recorders of riverine environmental variation

NASA Astrophysics Data System (ADS)

Kukolich, S.; Kendall, C.; Dettman, D. L.

2017-12-01

The geochemical record stored in growth increments of freshwater mussel shells reveals annual to sub-annual changes in environmental conditions during the lifetime of the organism. The carbon, nitrogen, and oxygen stable isotope composition of aragonite shells responds to changes in water chemistry, temperature, streamflow, turbidity, growth rate, size, age, and reproduction. The goals of this study are to determine how stable isotopes can be used to reconstruct the conditions in which the mussels lived and to illuminate any vital effects that might obscure the isotopic record of those conditions. Previous research has suggested that annual δ13C values decrease in older freshwater mussel shells due to lower growth rates and greater incorporation of dietary carbon into the shell with increasing age. However, a high-resolution, seasonal investigation of δ13C, δ15N, and δ18O as they relate to organism age has not yet been attempted in freshwater mussels. A total of 28 Unionid mussels of three different species were collected live in 2011 in the Tennessee River near Paducah, Kentucky, USA. In this study, we analyzed the shell nacre and external organic layers for stable carbon, nitrogen, and oxygen isotope ratios, focusing on growth bands formed between 2006 and 2011. We present a time series of shell δ13C, δ18O, and δ15N values with monthly resolution. We also compare the shell-derived geochemical time series to a time series of the δ13C and δ15N of particulate organic matter, δ13C of DIC, δ18OWater, and water temperature in which the mussels lived. Results show that environmental factors such as water temperature and primary productivity dominate shell chemistry while animal age has little or no effect.

The isotopic biosignatures of photo- vs. thiotrophic bivalves: are they preserved in fossil shells?

PubMed

Dreier, A; Loh, W; Blumenberg, M; Thiel, V; Hause-Reitner, D; Hoppert, M

2014-09-01

Symbiont-bearing and non-symbiotic marine bivalves were used as model organisms to establish biosignatures for the detection of distinctive symbioses in ancient bivalves. For this purpose, the isotopic composition of lipids (δ13C) and bulk organic shell matrix (δ13C, δ34S, δ15N) from shells of several thiotrophic, phototrophic, or non-symbiotic bivalves were compared (phototrophic: Fragum fragum, Fragum unedo, Tridacna maxima; thiotrophic: Codakia tigerina, Fimbria fimbriata, Anodontia sp.; non-symbiotic: Tapes dorsatus, Vasticardium vertebratum, Scutarcopagia sp.). ∆13C values of bulk organic shell matrices, most likely representing mainly original shell protein/chitin biomass, were depleted in thio- and phototrophic bivalves compared to non-symbiotic bivalves. As the bulk organic shell matrix also showed a major depletion of δ15N (down to -2.2 ‰) for thiotrophic bivalves, combined δ13C and δ15N values are useful to differentiate between thio-, phototrophic, and non-symbiotic lifestyles. However, the use of these isotopic signatures for the study of ancient bivalves is limited by the preservation of the bulk organic shell matrix in fossils. Substantial alteration was clearly shown by detailed microscopic analyses of fossil (late Pleistocene) T. maxima and Trachycardium lacunosum shell, demonstrating a severe loss of quantity and quality of bulk organic shell matrix with time. Likewise, the composition and δ13C-values of lipids from empty shells indicated that a large part of these compounds derived from prokaryotic decomposers. The use of lipids from ancient shells for the reconstruction of the bivalve's life style therefore appears to be restricted. © 2014 John Wiley & Sons Ltd.

Effects of angiotensin-II receptor blocker candesartan cilexetil in rats with dilated cardiomyopathy.

PubMed

Shirai, Ken; Watanabe, Kenichi; Ma, Meilei; Wahed, Mir I I; Inoue, Mikio; Saito, Yuki; Suresh, Palaniyandi Selvaraj; Kashimura, Takeshi; Tachikawa, Hitoshi; Kodama, Makoto; Aizawa, Yoshifusa

2005-01-01

We examined effects of an angiotensin-II receptor blockers, candesartan cilexetil, in rats with dilated cardiomyopathy after autoimmune myocarditis. Candesartan cilexetil showed angiotensin-II blocking action in a dose-dependent manner in rats with dilated cardiomyopathy. Twenty-eight days after immunization, surviving Lewis rats were divided into four groups and given candesartan cilexetil at 0.05 mg/kg, 0.5 mg/kg or 5 mg/kg per day (Group-C0.05, n = 15, Group-C0.5, n = 15 and Group-C5, n = 15, respectively) or vehicle alone (Group-V, n = 15). After oral administration for 1 month, the left ventricular end-diastolic pressure and heart weight/body weight ratio were lower in Group-C0.05 (13.3+/-1.1 mmHg and 3.7+/-0.2 g/kg, respectively), in Group-C0.5 (8.0+/-0.9 mmHg and 3.3+/-0.1 g/kg, respectively) and in Group-C5 (5.5+/-1 mmHg and 3.1+/-0.1 g/kg, respectively) than in Group-V (13.5+/-1.0 mmHg and 3.8+/-0.2 g/kg, respectively). The area of myocardial fibrosis was also lower in Group-C0.05 (25+/-3%), in Group-C0.5 (20+/-3%), and in Group-C5 (12+/-1%) than in Group-V (32+/-4%). Furthermore, expressions of transforming growth factor-beta1 and collagen-III mRNA were suppressed in Group-C0.05 (349+/-23% and 395+/-22%, respectively), Group-C0.5 (292+/-81% and 364+/-42%, respectively) and in Group-C5 (204+/-63% and 259+/-33%, respectively) compared with those in Group-V (367+/-26% and 437+/-18%, respectively). These results suggest that candesartan cilexetil can improve the function of inefficient heart.

Resource Utilization by Native and Invasive Earthworms and Their Effects on Soil Carbon and Nitrogen Dynamics in Puerto Rican Soils

Treesearch

Ching-Yu Huang; Grizelle Gonzalez; Paul F. Hendrix

2016-01-01

Resource utilization by earthworms affects soil C and N dynamics and further colonization of invasive earthworms. By applying 13C-labeled Tabebuia heterophylla leaves and 15N-labeled Andropogon glomeratus grass, we investigated resource utilization by three earthworm species (...

Fate of organo-mineral particles in streams: Microbial degradation by streamwater & biofilm assemblages

NASA Astrophysics Data System (ADS)

Hunter, W. R.; Raich, M.; Wanek, W.; Battin, T. J.

2013-12-01

Inland waters are of global biogeochemical importance. They receive carbon inputs of ~ 4.8 Pg C/ y of which, 12 % is buried, 18 % transported to the oceans, and 70 % supports aquatic secondary production. However, the mechanisms that determine the fate of organic matter (OM) in these systems are poorly defined. One aspect of this is the formation of organo-mineral complexes in aquatic systems and their potential as a route for OM transport and burial vs. their use as carbon (C) and nitrogen (N) sources within aquatic systems. Organo-mineral particles form by sorption of dissolved OM to freshly eroded mineral surfaces and may contribute to ecosystem-scale particulate OM fluxes. We experimentally tested the availability of mineral-sorbed OM as a C & N source for streamwater microbial assemblages and streambed biofilms. Organo-mineral particles were constructed in vitro by sorption of 13C:15N-labelled amino acids to hydrated kaolin particles, and microbial degradation of these particles compared with equivalent doses of 13C:15N-labelled free amino acids. Experiments were conducted in 120 ml mesocosms over 7 days using biofilms and water sampled from the Oberer Seebach stream (Austria). Each incubation experienced a 16:8 light:dark regime, with metabolism monitored via changes in oxygen concentrations between photoperiods. The relative fate of the organo-mineral particles was quantified by tracing the mineralization of the 13C and 15N labels and their incorporation into microbial biomass. Here we present the initial results of 13C-label mineralization, incorporation and retention within dissolved organic carbon pool. The results indicate that 514 (× 219) μmol/ mmol of the 13:15N labeled free amino acids were mineralized over the 7-day incubations. By contrast, 186 (× 97) μmol/ mmol of the mineral-sorbed amino acids were mineralized over a similar period. Thus, organo-mineral complexation reduced amino acid mineralization by ~ 60 %, with no differences observed between the streamwater and biofilm assemblages. Throughout the incubations, biofilms were observed to leach dissolved organic carbon (DOC). However, within the streamwater assemblage the presence of both organo-mineral particles and kaolin particles was associated with significant DOC removal (-1.7 % and -7.5 % respectively). Consequently, the study demonstrates that mineral and organo-mineral particles can limit the availability of DOC in aquatic systems, providing nucleation sites for flocculation and fresh mineral surfaces, which facilitate OM-sorption. The formation of these organo-mineral particles subsequently restricts microbial OM degradation, potentially altering the transport and facilitating the burial of OM within streams.

The Supply of Women Enlistees and Their Utilization in the Navy

DTIC Science & Technology

1976-06-01

to achieve." 11The importance of the role played by the uniform is pointed out by Nathan Joseph and Nicholas Alex. "The Uniform: A Sociological Per...kindergarten) 12.20 14 12.47 5.51 15. Nurse (practical) 14.50 15 13.82 6.38 16. Professional musician (dance orchestra) 14.95 16 14.84 6.54 17. Steno -Typist

Minot AFB, North Dakota. Revised Uniform Summary of Surface Weather Observations (RUSSWO). Parts A-F.

DTIC Science & Technology

1987-12-01

MAC) REVISED UNIFORM SUMMARY OF SURFACE WEATHER OBSERVATIONS MINOT AFB ND MSC 727675 N 48 25 W 101 21 ELEV 1668 FT KMIB PARTS A - F HOURS SUMMARIZED...o . ... . . . . .. . * , . .*** . *.,, ,,.* .. OrALt NtUME3P OP OE sERvI TO js: uC 6 LOYlAL CLIMPIATIOLO0G Y BAp AN(CH Pt QLI 1.T1A(.E It L...OF P1- COPD : 7 7-P6 MONTH: OCT IHOUPS(LSTI: ALL I wIND SPCFJ3 IN KN015 DIPECTIIN 1-3 4-6 7-10 11-16 17-21 227 28-33 34-40 41-47 4F-1S GE S6 TCI&L MEAt

Formation and acceleration of uniformly filled ellipsoidal electron bunches obtained via space-charge-driven expansion from a cesium-telluride photocathode

NASA Astrophysics Data System (ADS)

Piot, P.; Sun, Y.-E.; Maxwell, T. J.; Ruan, J.; Secchi, E.; Thangaraj, J. C. T.

2013-01-01

We report the experimental generation, acceleration, and characterization of a uniformly filled electron bunch obtained via space-charge-driven expansion (often referred to as “blow-out regime”) in an L-band (1.3-GHz) radiofrequency photoinjector. The beam is photoemitted from a cesium-telluride semiconductor photocathode using a short (<200fs) ultraviolet laser pulse. The produced electron bunches are characterized with conventional diagnostics and the signatures of their ellipsoidal character are observed. We especially demonstrate the production of ellipsoidal bunches with charges up to ˜0.5nC corresponding to a ˜20-fold increase compared to previous experiments with metallic photocathodes.

The 12C/13C Ratio in Sgr B2(N): Constraints for Galactic Chemical Evolution and Isotopic Chemistry

NASA Astrophysics Data System (ADS)

Halfen, D. T.; Woolf, N. J.; Ziurys, L. M.

2017-08-01

A study has been conducted of 12C/13C ratios in five complex molecules in the Galactic center. H2CS, CH3CCH, NH2CHO, CH2CHCN, and CH3CH2CN and their 13C-substituted species have been observed in numerous transitions at 1, 2, and 3 mm, acquired in a spectral-line survey of Sgr B2(N), conducted with the telescopes of the Arizona Radio Observatory (ARO). Between 22 and 54 individual, unblended lines for the 12C species and 2-54 for 13C-substituted analogs were modeled in a global radiative transfer analysis. All five molecules were found to consistently exhibit two velocity components near V LSR ˜ 64 and 73 km s-1, with column densities ranging from N tot ˜ 3 × 1014 - 4 × 1017 cm-2 and ˜2 × 1013 - 1 × 1017 cm-2 for the 12C and 13C species, respectively. Based on 14 different isotopic combinations, ratios were obtained in the range 12C/13C = 15 ± 5 to 33 ± 13, with an average value of 24 ± 7, based on comparison of column densities. These measurements better anchor the 12C/13C ratio at the Galactic center, and suggest a slightly revised isotope gradient of 12C/13C = 5.21(0.52) D GC + 22.6(3.3). As indicated by the column densities, no preferential 13C enrichment was found on the differing carbon sites of CH3CCH, CH2CHCN, and CH3CH2CN. Because of the elevated temperatures in Sgr B2(N), 13C isotopic substitution is effectively “scrambled,” diminishing chemical fractionation effects. The resulting ratios thus reflect stellar nucleosynthesis and Galactic chemical evolution, as is likely the case for most warm clouds.

Elucidating proline dynamics in spider dragline silk fibre using 2H-13C HETCOR MAS NMR.

PubMed

Shi, Xiangyan; Yarger, Jeffery L; Holland, Gregory P

2014-05-14

(2)H-(13)C HETCOR MAS NMR is performed on (2)H/(13)C/(15)N-Pro enriched A. aurantia dragline silk. Proline dynamics are extracted from (2)H NMR line shapes and T1 in a site-specific manner to elucidate the backbone and side chain molecular dynamics for the MaSp2 GPGXX β-turn regions for spider dragline silk in the dry and wet, supercontracted states.

Molecular and bulk isotopic analyses of organic matter in marls of the Mulhouse Basin (Tertiary, Alsace, France)

NASA Technical Reports Server (NTRS)

Hollander, D. J.; Sinninghe Damste, J. S.; Hayes, J. M.; de Leeuw, J. W.; Huc, A. Y.

1993-01-01

Contents of 13C in kerogens and carbonates in 21 samples from a core of the MAX borehole, Mulhouse Evaporite Basin, range from -27.3 to -23.5 and -3.7 to -1.8% vs PDB, respectively. Organic nitrogen in the same samples is enriched in 15N relative to atmospheric N2 by 12.2-15.7%. Hydrogen indices and delta values for kerogens vary systematically with facies, averaging 493 mg HC/g Corg and -25.7% in the most saline facies (dominated by inputs from aquatic sources) and 267 mg HC/g Corg and -23.7% in the least saline facies (50/50 aquatic/terrigenous). Values of delta were measured for individual aliphatic hydrocarbons from three samples representing three different organic facies. For all samples, terrigenous inputs were unusually rich in 13C, the estimated delta value for bulk terrigenous debris, apparently derived partly from CAM plants, being -22.5%. In the most saline facies, isotopic evidence indicates the mixing of 13C-depleted products of photosynthetic bacteria with 13C-enriched products of halotolerant eukaryotic algae. At lower salinities, a change in the producer community is marked by a decrease in the 13C content of algal lipids. The content of 13C in algal lipids increases in the least saline facies, due either to succession of different organisms or to decreased concentrations of dissolved CO2.

Terrestrial and marine trophic pathways support young-of-year growth in a nearshore Arctic fish

USGS Publications Warehouse

von Biela, Vanessa R.; Zimmerman, Christian E.; Cohn, Brian R.; Welker, Jeffrey M.

2013-01-01

River discharge supplies nearshore communities with a terrestrial carbon source that is often reflected in invertebrate and fish consumers. Recent studies in the Beaufort Sea have documented widespread terrestrial carbon use among invertebrates, but only limited use among nearshore fish consumers. Here, we examine the carbon source and diet of rapidly growing young-of-year Arctic cisco (Coregonus autumnalis) using stable isotope values (δ13C and δ15N) from muscle and diet analysis (stomach contents) during a critical and previously unsampled life stage. Stable isotope values (δ15N and δ13C) may differentiate between terrestrial and marine sources and integrate over longer time frames (weeks). Diet analysis provides species-specific information, but only from recent foraging (days). Average δ13C for all individuals was −25.7 ‰, with the smallest individuals possessing significantly depleted δ13C values indicative of a stronger reliance of terrestrial carbon sources as compared to larger individuals. Average δ15N for all individuals was 10.4 ‰, with little variation among individuals. As fish length increased, the proportion of offshore Calanus prey and neritic Mysis prey increased. Rapid young-of-year growth in Arctic cisco appears to use terrestrial carbon sources obtained by consuming a mixture of neritic and offshore zooplankton. Shifts in the magnitude or phenology of river discharge and the delivery of terrestrial carbon may alter the ecology of nearshore fish consumers.

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.

The impact of Great Cormorants on biogenic pollution of land ecosystems: Stable isotope signatures in small mammals.

PubMed

Balčiauskas, Linas; Skipitytė, Raminta; Jasiulionis, Marius; Trakimas, Giedrius; Balčiauskienė, Laima; Remeikis, Vidmantas

2016-09-15

Studying the isotopic composition of the hair of two rodent species trapped in the territories of Great Cormorant colonies, we aimed to show that Great Cormorants transfer biogens from aquatic ecosystems to terrestrial ecosystems, and that these substances reach small mammals through the trophic cascade, thus influencing the nutrient balance in the terrestrial ecosystem. Analysis of δ(13)C and δ(15)N was performed on two dominant species of small mammals, Apodemus flavicollis and Myodes glareolus, inhabiting the territories of the colonies. For both species, the values of δ(13)C and δ(15)N were higher in the animals trapped in the territories of the colonies than those in control territories. In the hair of A. flavicollis and M. glareolus, the highest values of δ(15)N (16.31±3.01‰ and 17.86±2.76‰, respectively) were determined in those animals trapped in the biggest Great Cormorant colony. δ(15)N values were age dependent, highest in adult A. flavicollis and M. glareolus and lowest in juvenile animals. For δ(13)C values, age-dependent differences were not registered. δ(15)N values in both small mammal species from the biggest Great Cormorant colony show direct dependence on the intensity of influence. Biogenic pollution is at its strongest in the territories of the colonies with nests, significantly diminishing in the ecotones of the colonies and further in the control zones, where the influence of birds is negligible. Thus, Great Cormorant colonies alter ecosystem functioning by enrichment with biogens, with stable isotope values in small mammals significantly higher in the affected territories. Copyright © 2016 Elsevier B.V. All rights reserved.

Bridge over troubled proline: assignment of intrinsically disordered proteins using (HCA)CON(CAN)H and (HCA)N(CA)CO(N)H experiments concomitantly with HNCO and i(HCA)CO(CA)NH.

PubMed

Hellman, Maarit; Piirainen, Henni; Jaakola, Veli-Pekka; Permi, Perttu

2014-01-01

NMR spectroscopy is by far the most versatile and information rich technique to study intrinsically disordered proteins (IDPs). While NMR is able to offer residue level information on structure and dynamics, assignment of chemical shift resonances in IDPs is not a straightforward process. Consequently, numerous pulse sequences and assignment protocols have been developed during past several years, targeted especially for the assignment of IDPs, including experiments that employ H(N), H(α) or (13)C detection combined with two to six indirectly detected dimensions. Here we propose two new HN-detection based pulse sequences, (HCA)CON(CAN)H and (HCA)N(CA)CO(N)H, that provide correlations with (1)H(N)(i - 1), (13)C'(i - 1) and (15)N(i), and (1)H(N)(i + 1), (13)C'(i) and (15)N(i) frequencies, respectively. Most importantly, they offer sequential links across the proline bridges and enable filling the single proline gaps during the assignment. We show that the novel experiments can efficiently complement the information available from existing HNCO and intraresidual i(HCA)CO(CA)NH pulse sequences and their concomitant usage enabled >95 % assignment of backbone resonances in cytoplasmic tail of adenosine receptor A2A in comparison to 73 % complete assignment using the HNCO/i(HCA)CO(CA)NH data alone.

Paleoecology reconstruction from trapped gases in a fulgurite from the late Pleistocene of the Libyan Desert

USGS Publications Warehouse

Navarro, Gonzalez R.; Mahan, S.A.; Singhvi, A.K.; Navarro-Aceves, R.; Rajot, J.-L.; McKay, C.P.; Coll, P.; Raulin, F.

2007-01-01

When lightning strikes the ground, it heats, melts, and fuses the sand in soils to form glass tubes known as fulgurites. We report here the composition of CO2, CO, and NO contained within the glassy bubbles of a fulgurite from the Libyan Desert. The results show that the fulgurite formed when the ground contained 0.1 wt% organic carbon with a C/N ratio of 10-15 and a ??13C of -13.96???, compositions similar to those found in the present-day semiarid region of the Sahel, where the vegetation is dominated by C4, plants. Thermoluminescence dating indicates that this fulgurite formed ???15 k.y. ago. These results imply that the semiarid Sahel (at 17??N) reached at least to 24??N at this time, and demonstrate that fulgurite gases and luminescence geochronology can be used in quantitative paleoecology. ?? 2007 Geological Society of America.

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

PubMed Central

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

2017-01-01

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

In Vivo Isotopic Labeling of Symbiotic Bacteria Involved in Cellulose Degradation and Nitrogen Recycling within the Gut of the Forest Cockchafer (Melolontha hippocastani).

PubMed

Alonso-Pernas, Pol; Bartram, Stefan; Arias-Cordero, Erika M; Novoselov, Alexey L; Halty-deLeon, Lorena; Shao, Yongqi; Boland, Wilhelm

2017-01-01

The guts of insects harbor symbiotic bacterial communities. However, due to their complexity, it is challenging to relate a specific symbiotic phylotype to its corresponding function. In the present study, we focused on the forest cockchafer ( Melolontha hippocastani ), a phytophagous insect with a dual life cycle, consisting of a root-feeding larval stage and a leaf-feeding adult stage. By combining in vivo stable isotope probing (SIP) with 13 C cellulose and 15 N urea as trophic links, with Illumina MiSeq (Illumina-SIP), we unraveled bacterial networks processing recalcitrant dietary components and recycling nitrogenous waste. The bacterial communities behind these processes change between larval and adult stages. In 13 C cellulose-fed insects, the bacterial families Lachnospiraceae and Enterobacteriaceae were isotopically labeled in larvae and adults, respectively. In 15 N urea-fed insects, the genera Burkholderia and Parabacteroides were isotopically labeled in larvae and adults, respectively. Additionally, the PICRUSt-predicted metagenome suggested a possible ability to degrade hemicellulose and to produce amino acids of, respectively, 13 C cellulose- and 15 N urea labeled bacteria. The incorporation of 15 N from ingested urea back into the insect body was confirmed, in larvae and adults, by isotope ratio mass spectrometry (IRMS). Besides highlighting key bacterial symbionts of the gut of M. hippocastani , this study provides example on how Illumina-SIP with multiple trophic links can be used to target microorganisms embracing different roles within an environment.

Application of SAIL phenylalanine and tyrosine with alternative isotope-labeling patterns for protein structure determination.

PubMed

Takeda, Mitsuhiro; Ono, Akira M; Terauchi, Tsutomu; Kainosho, Masatsune

2010-01-01

The extensive collection of NOE constraint data involving the aromatic ring signals is essential for accurate protein structure determination, although it is often hampered in practice by the pervasive signal overlapping and tight spin couplings for aromatic rings. We have prepared various types of stereo-array isotope labeled phenylalanines (epsilon- and zeta-SAIL Phe) and tyrosine (epsilon-SAIL Tyr) to overcome these problems (Torizawa et al. 2005), and proven that these SAIL amino acids provide dramatic spectral simplification and sensitivity enhancement for the aromatic ring NMR signals. In addition to these SAIL aromatic amino acids, we recently synthesized delta-SAIL Phe and delta-SAIL Tyr, which allow us to observe and assign delta-(13)C/(1)H signals very efficiently. Each of the various types of SAIL Phe and SAIL Tyr yields well-resolved resonances for the delta-, epsilon- or zeta-(13)C/(1)H signals, respectively, which can readily be assigned by simple and robust pulse sequences. Since the delta-, epsilon-, and zeta-proton signals of Phe/Tyr residues give rise to complementary NOE constraints, the concomitant use of various types of SAIL-Phe and SAIL-Tyr would generate more accurate protein structures, as compared to those obtained by using conventional uniformly (13)C, (15)N-double labeled proteins. We illustrated this with the case of an 18.2 kDa protein, Escherichia coli peptidyl-prolyl cis-trans isomerase b (EPPIb), and concluded that the combined use of zeta-SAIL Phe and epsilon-SAIL Tyr would be practically the best choice for protein structural determinations.

Plant family identity distinguishes patterns of carbon and nitrogen stable isotope abundance and nitrogen concentration in mycoheterotrophic plants associated with ectomycorrhizal fungi

PubMed Central

Hynson, Nicole A.; Schiebold, Julienne M.-I.; Gebauer, Gerhard

2016-01-01

Background and Aims Mycoheterotrophy entails plants meeting all or a portion of their carbon (C) demands via symbiotic interactions with root-inhabiting mycorrhizal fungi. Ecophysiological traits of mycoheterotrophs, such as their C stable isotope abundances, strongly correlate with the degree of species’ dependency on fungal C gains relative to C gains via photosynthesis. Less explored is the relationship between plant evolutionary history and mycoheterotrophic plant ecophysiology. We hypothesized that the C and nitrogen (N) stable isotope compositions, and N concentrations of fully and partially mycoheterotrophic species differentiate them from autotrophs, and that plant family identity would be an additional and significant explanatory factor for differences in these traits among species. We focused on mycoheterotrophic species that associate with ectomycorrhizal fungi from plant families Ericaceae and Orchidaceae. Methods Published and unpublished data were compiled on the N concentrations, C and N stable isotope abundances (δ13C and δ15N) of fully (n = 18) and partially (n = 22) mycoheterotrophic species from each plant family as well as corresponding autotrophic reference species (n = 156). These data were used to calculate site-independent C and N stable isotope enrichment factors (ε). Then we tested for differences in N concentration, 13C and 15N enrichment among plant families and trophic strategies. Key Results We found that in addition to differentiating partially and fully mycoheterotrophic species from each other and from autotrophs, C and N stable isotope enrichment also differentiates plant species based on familial identity. Differences in N concentrations clustered at the plant family level rather than the degree of dependency on mycoheterotrophy. Conclusions We posit that differences in stable isotope composition and N concentrations are related to plant family-specific physiological interactions with fungi and their environments. PMID:27451987

Enzyme induction in neonates after fetal exposure to antiepileptic drugs

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

Rating, D.; Jaeger-Roman, E.; Nau, H.

1983-01-01

The /sup 13/C-AP breath test is shown to be a convenient, noninvasive method to monitor velocity and capacity of P450-dependent AP N-demethylation in infancy and childhood. According to /sup 13/C-AP breath tests, neonates have a very low capacity to eliminate /sup 13/CO/sub 2/, which is only 15 to 21% of the activity in adults. During the first year of life AP N-demethylation increases to reach its maximum at about 2 years; afterwards a slight decrease occurs. In 25 neonates exposed prenatally to different antiepileptic drugs /sup 13/C-AP breath test was efficiently used to prove that cytochrome AP N-demethylation was considerablymore » stimulated. After primidone/phenobarbitone, especially in combination with phenytoin, /sup 13/C elimination reaches and even surpasses the range for older children. Valproate exposure during fetal life is not consistently followed by a significant increase in AP N-demethylation. The enzyme induction demonstrated by /sup 13/C-AP breath test was often accompanied by accelerated metabolic clearance and shortened half-life times of transplacentally acquired antiepileptic drugs. There was good agreement between /sup 13/C-AP breath tests and pharmacokinetic data for primidone/phenobarbitone but not for phenytoin. In contrast, in the case of phenytoin exposure during pregnancy the pharmacokinetic parameters and the /sup 13/C breath test data will transport very different informations about enzyme induction in these neonates.« less

Biological Degradation of Black Carbon in Temperate Forest Soils: Effects of Clay Mineralogy and Nitrogen Availability

NASA Astrophysics Data System (ADS)

Bird, J. A.; Santos, F.; Torn, M. S.

2008-12-01

A critical knowledge gap in soil organic carbon (SOC) cycling concerns the SOC portion collectively known as pyrogenic C or black carbon (BC), which is a chemically heterogeneous class of highly reduced compounds produced by incomplete combustion. While the stocks of BC are significant in surface soils worldwide, this SOC pool has been considered to be relatively inert with negligible biologically mediated degradation of BC occurring. We will present findings from a laboratory incubation of dual-labeled (13C/15N) BC and its precursor wood (Pinus ponderosa) in two temperate soils (Haploxeralfs) that differ in their clay mineralogy (granitic versus andesitic parent material) and organic C content. In addition, we used N additions in the granitic soil to investigate the effects of N availability on soil and substrate C and N cycling. Sterile controls were used to demonstrate that the BC turnover observed was biotic. The laboratory incubations were carried out at 25°C and at 55% of soil water holding capacity. We are measuring the flux of mineralized 13C in respired CO2, dissolved organic C, soil microbial biomass, specific microbial groups (13C-phospholipid fatty acids) and density-defined soil organic matter fractions. The overall flux of 15N is being observed in the microbial biomass, soluble organic and inorganic pools, and organic matter fractions. We will present rates of biologically-mediated decomposition of BC and its precursor wood, as well as the effects of soil mineralogy and N availability on these rates and on products of decomposition. We will also present decomposition rates of native SOM in incubations with and without substrate to investigate C priming.

High-resolution quantitative imaging of mammalian and bacterial cells using stable isotope mass spectrometry.

PubMed

Lechene, Claude; Hillion, Francois; McMahon, Greg; Benson, Douglas; Kleinfeld, Alan M; Kampf, J Patrick; Distel, Daniel; Luyten, Yvette; Bonventre, Joseph; Hentschel, Dirk; Park, Kwon Moo; Ito, Susumu; Schwartz, Martin; Benichou, Gilles; Slodzian, Georges

2006-01-01

Secondary-ion mass spectrometry (SIMS) is an important tool for investigating isotopic composition in the chemical and materials sciences, but its use in biology has been limited by technical considerations. Multi-isotope imaging mass spectrometry (MIMS), which combines a new generation of SIMS instrument with sophisticated ion optics, labeling with stable isotopes, and quantitative image-analysis software, was developed to study biological materials. The new instrument allows the production of mass images of high lateral resolution (down to 33 nm), as well as the counting or imaging of several isotopes simultaneously. As MIMS can distinguish between ions of very similar mass, such as 12C15N- and 13C14N-, it enables the precise and reproducible measurement of isotope ratios, and thus of the levels of enrichment in specific isotopic labels, within volumes of less than a cubic micrometer. The sensitivity of MIMS is at least 1,000 times that of 14C autoradiography. The depth resolution can be smaller than 1 nm because only a few atomic layers are needed to create an atomic mass image. We illustrate the use of MIMS to image unlabeled mammalian cultured cells and tissue sections; to analyze fatty-acid transport in adipocyte lipid droplets using 13C-oleic acid; to examine nitrogen fixation in bacteria using 15N gaseous nitrogen; to measure levels of protein renewal in the cochlea and in post-ischemic kidney cells using 15N-leucine; to study DNA and RNA co-distribution and uridine incorporation in the nucleolus using 15N-uridine and 81Br of bromodeoxyuridine or 14C-thymidine; to reveal domains in cultured endothelial cells using the native isotopes 12C, 16O, 14N and 31P; and to track a few 15N-labeled donor spleen cells in the lymph nodes of the host mouse. MIMS makes it possible for the first time to both image and quantify molecules labeled with stable or radioactive isotopes within subcellular compartments.

7 CFR 3015.13 - Minority and women-owned banks.

Code of Federal Regulations, 2010 CFR

2010-01-01

... 7 Agriculture 15 2010-01-01 2010-01-01 false Minority and women-owned banks. 3015.13 Section 3015.13 Agriculture Regulations of the Department of Agriculture (Continued) OFFICE OF THE CHIEF FINANCIAL OFFICER, DEPARTMENT OF AGRICULTURE UNIFORM FEDERAL ASSISTANCE REGULATIONS Cash Depositories § 3015.13...

The second wave of earthworm invasion: soil organic matter dynamics from the stable isotope perspective

NASA Astrophysics Data System (ADS)

Chang, C.; Szlavecz, K. A.; Bernard, M.; Pitz, S.

2013-12-01

Through transformation of plant litter into soil organic matter (SOM) and translocation of ingested organic material among different soil depths, soil organisms, especially earthworms, are one of the major factors affecting SOM dynamics. In North America temperate soil, historical human activity has lead to invasion of European earthworms into habitats that were previously earthworm-free or inhabited only by native species. By consuming leaf litter and SOM, burrowing, and casting, invasive earthworms have been known for reducing the understory vegetation and leaf litter layer while increasing the thickness of organic soil, causing changes in the soil habitat and the distribution of SOM. Recently, another group of invasive earthworm, namely Amynthas from Asia, has been reported invading habitats already dominated by European species, causing a 'second wave of invasion' where the soil ecosystem, already modified by European species, is going through another transition. The mechanisms through which these functionally (ecologically) different species affect C and N transformation could be better understood by tracing the carbon and nitrogen derived from 13C- and 15N-labeled leaf litter into earthworm tissues and SOM. The objective of this study is to understand how earthworm species that differ ecologically, including the Asian Amynthas, interact with each other and how these interactions affect SOM dynamics. We hypothesized that 1) species feeding on different food resources will have different isotopic signature and their tissue 13C and 15N values will change due to facilitation or interspecific competition on food resources, and 2) the short-term fate of litter-derived carbon differs depending on the presence or absence of different earthworm species. These hypotheses were tested by field sampling and lab mesocosm experiments using 13C and 15N double-enriched Tulip Poplar leaf litter (mean 13C = 124‰, mean 15N = 1667‰) produced from tree saplings growing in an airtight chamber. Stable isotope mass balance calculation is used to estimate the recovery of litter-derived carbon from three pools (earthworm tissue, SOM, remaining litter), the loss of litter-derived carbon through soil respiration, and the contribution of different carbon sources to soil CO2 efflux in different earthworm treatments. Our results show that earthworm species recognized as 'soil feeders' have 13C and 15N values that are 1.2‰ and 3.8‰ higher than those of 'litter feeders', and 15N also differ significantly amount different soil feeders, suggesting different food resource usage even within the same functional group. There are strong species effects on both leaf litter disappearance rate and CO2 efflux rate, both being high when Amynthas earthworms are present. Our results suggest that changing earthworm species composition leads to changing resource use, which alters the fate of organic carbon in the forest floor and soil and could potentially affect long-term SOM dynamics in temperate forests.

Quantum chemical study on the NLO and NBO properties of 4-hydroxy quinoline-2-carboxylic acid

NASA Astrophysics Data System (ADS)

Pattanayak, Subrat Kumar

2018-05-01

The nonlinear optical properties and natural bond analysis properties, different global chemical reactivity properties of the compound 4-hydroxy quinoline-2-carboxylic acid are studied by density function theory. The dipole moment (μ) and linear polarizability are found 1.60259 D and 15.138×10-24esu respectively. A comparatively greater value dipole moment 1.46154 D is obtained in direction of μy. It was observed the interaction energies of acceptor of NBO C1 - C2 and donor C5 - C6, NBO of C13 - N15 and C9 - C12, NBO of C13 - N15 and C18 - O21, NBO of O19 and C18 - O21 are 30.92, 358.86, 320.39, 58.55 Kcal/mol. We are getting the low ionization energy 7.033 electron volt (eV) for the studied molecule, which indicates the high inhibition efficiency. Here we note that, high value of ionisation energy indicating the high stability as well as inertness of that molecule. The HOMO and LUMO energies are found -7.033 eV and -2.5212 eV respectively.

MacDill AFB, Tampa Bay, Florida. Revised Uniform Summary of Surface Weather Observations (RUSSWO). Parts A-F

DTIC Science & Technology

1980-03-05

3.1 __ __ 3.1 900 1.5-17 .4 1.3 ____1.3 .1 1.9 1.9 899 c 18 -20 .2 __ 1. 26 21-23 .2 1.3 _____ __ 1.3 .6 2.0 1__ 2.4f 900 __ Rs___ 7.0.L719 03 1 1 28...930 0-1 18 3.81_ 3*8 1.613 41 14.0 930 - 12-14 1.? 5.51 SOB_ &. 4 5.659 930 0 15-17 4.1 4.9 4.91 *1 3.8 3.8 930 18 -20 4.0 S*b_______ 5.6 __ _ 3.3 13.31...7440 DE -5 So$ 5_8 90I* 18 73 SEP 4.0 *13 __0_5. 1.91 6.9I 79 -*. -.- -- s -5 73 O-AC ___ .73S35 28 5466 73 NOV ___ .2 .2 ____ 2.2 7.1* 6.410.9 720

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

PubMed Central

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

1984-01-01

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

Carbon and nitrogen isotope ratios of juvenile winter flounder ...

EPA Pesticide Factsheets

Stable carbon and nitrogen isotope ratios were measured in the muscle tissues of young-of-the-year (YOY) winter flounder, Pseudopleuronectes americanus, collected from several estuarine systems along the coast of Rhode Island, USA. These systems included three coastal lagoons (Ninigret Pond, Green Hill Pond and Point Judith Pond), an estuarine river (Narrow River) and Narragansett Bay. Results from sampling over a three-year period showed some year-to-year variability for 13C within waterbodies; however, 15N values were not significantly different (P > 0.05) within systems among the three years studied. he 13C trends observed along transects in Narrow River and Narragansett Bay showed isotopically depleted terrestrial signals in the upper reaches of the estuaries and more positive values indicative of marine organic material in the lower regions of these systems. Significant differences (P < 0.05) in 15N were observed among estuarine systems. Fish from the coastal lagoons had the lowest 15N values followed by those from Narrow River and then Narragansett Bay. Some unexpected trends in 15N were observed within Narragansett Bay. The Bay has a strong north-south gradient in nutrient concentrations due to large sewage inputs in the upper Bay which was not reflected in flounder 15N values. As expected, YOY flounder from stations in the lower-Bay had depleted 15N values compared to those from the other locations. However, the 15N ratios o

Analysis of concentration and (13)C enrichment of D-galactose in human plasma.

PubMed

Schadewaldt, P; Hammen, H W; Loganathan, K; Bodner-Leidecker, A; Wendel, U

2000-05-01

A stable-isotope dilution method for the sensitive determination of D-galactose in human plasma was established. D-[(13)C]Galactose was added to plasma, and the concentration was measured after D-glucose was removed from the plasma by treatment with D-glucose oxidase and the sample was purified by ion-exchange chromatography. For gas chromatographic-mass spectrometric analysis, aldononitrile pentaacetate derivatives were prepared. Monitoring of the [MH-60](+) ion intensities at m/z 328, 329, and 334 in the positive chemical ionization mode allowed the assessment of 1-(12)C-, 1-(13)C-, and U-(13)C(6)-labeled D-galactose, respectively. The D-galactose concentration was quantified on the basis of the (13)C-labeled internal standard. The method was linear (range examined, 0.1-5 micromol/L) and of good repeatability in the low and high concentration ranges (within- and between-run CVs <15%). The limit of quantification for plasma D-galactose was <0.02 micromol/L. Measurements in plasma of postabsorptive subjects yielded D-galactose concentrations (mean +/- SD) of 0.12 +/- 0.03 (n = 16), 0.11 +/- 0.04 (n = 15), 1.44 +/- 0.54 (n = 10), and 0.17 +/- 0.07 (n = 5) micromol/L in healthy adults, diabetic patients, patients with classical galactosemia, and obligate heterozygous parents thereof, respectively. These data were considerably lower (3- to 18-fold) than the values of a conventional enzymatic assay. The procedure was also applied successfully in a stable-isotope turnover study to evaluate endogenous D-galactose formation. The present findings establish that detection of D-galactose from endogenous sources is feasible in human plasma and show that erroneously high results may be obtained by enzymatic methods.

Structure elucidation of the designer drug N-(1-amino-3,3-dimethyl-1-oxobutan-2-yl)-1-(5-fluoropentyl)-3-(4-fluorophenyl)-pyrazole-5-carboxamide and the relevance of predicted (13) C NMR shifts - a case study.

PubMed

Girreser, Ulrich; Rösner, Peter; Vasilev, Andrej

2016-07-01

The detailed structure elucidation process of the new cannabimimetic designer drug, N-(1-amino-3,3-dimethyl-1-oxobutan-2-yl)-1-(5-fluoropentyl)-3-(4-fluorophenyl)-pyrazole-5-carboxamide, with a highly substituted pyrazole skeleton, using nuclear magnetic resonance (NMR) spectroscopic and mass spectrometric (MS) techniques is described. After a first analysis of the NMR spectra and comparison with 48 possible pyrazole and imidazole structures, a subset of six positional isomeric pyrazoles and six imidazoles remained conceivable. Four substituents of the heterocyclic skeleton were identified: a proton bound to a pyrazole ring carbon atom; a 5-fluoropentyl group; a 4-fluorophenyl substituent; and a carbamoyl group, which is N-substituted with a methyl residue carrying a tert.-butyl and a carbamoyl substituent. The 5-fluoropentyl residue is situated at the nitrogen ring atom. Additional NMR experiments like the (1) H,(13) C HMBC were performed, but due to the small number of signals based on long-range couplings, the comparison of predicted and observed (13) C chemical shifts became necessary. The open access Internet shift prediction programs NMRDB, NMRSHIFTDB2, and CSEARCH were employed for the prediction of (13) C shift values which allowed an efficient and unambiguous structure determination. For the identified N-(1-amino-3,3-dimethyl-1-oxobutan-2-yl)-1-(5-fluoropentyl)-3-(4-fluorophenyl)-pyrazole-5-carboxamide, the best agreement between predicted (13) C shifts and the observed chemical shifts and long-range couplings for the pyrazole ring carbon atoms, with a standard error of about 2 ppm, was found with each of the predictions. For the comparison of measured and predicted chemical shifts model compounds with simple substituents proved helpful. The identified compound is a homologue of AZ-037 which is offered by Internet suppliers. Copyright © 2015 John Wiley & Sons, Ltd. Copyright © 2015 John Wiley & Sons, Ltd.

Reorganization of a marine trophic network along an inshore-offshore gradient due to stronger pelagic-benthic coupling in coastal areas

NASA Astrophysics Data System (ADS)

Kopp, Dorothée; Lefebvre, Sébastien; Cachera, Marie; Villanueva, Maria Ching; Ernande, Bruno

2015-01-01

Recent theoretical considerations have highlighted the importance of the pelagic-benthic coupling in marine food webs. In continental shelf seas, it was hypothesized that the trophic network structure may change along an inshore-offshore gradient due to weakening of the pelagic-benthic coupling from coastal to offshore areas. We tested this assumption empirically using the eastern English Channel (EEC) as a case study. We sampled organisms from particulate organic matter to predatory fishes and used baseline-corrected carbon and nitrogen stable isotope ratios (δ13C and δ15N) to determine their trophic position. First, hierarchical clustering on δ13C and δ15N coupled to bootstrapping and estimates of the relative contribution of pelagic and benthic carbon sources to consumers' diet showed that, at mesoscale, the EEC food web forms a continuum of four trophic levels with trophic groups spread across a pelagic and a benthic trophic pathway. Second, based on the same methods, a discrete approach examined changes in the local food web structure across three depth strata in order to investigate the inshore-offshore gradient. It showed stronger pelagic-benthic coupling in shallow coastal areas mostly due to a reorganization of the upper consumers relative to the two trophic pathways, benthic carbon sources being available to pelagic consumers and, reciprocally, pelagic sources becoming accessible to benthic species. Third a continuous approach examined changes in the mean and variance of upper consumers' δ13C and δ15N with depth. It detected a significant decrease in δ13C variance and a significant increase in δ15N variance as depth increases. A theoretical two-source mixing model showed that an inshore-offshore decrease in the pelagic-benthic coupling was a sufficient condition to produce the δ13C variance pattern, thus supporting the conclusions of the discrete approach. These results suggest that environmental gradients such as the inshore-offshore one should be accounted for to better understand marine food webs dynamics.

Earth's magnetic field enabled scalar coupling relaxation of 13C nuclei bound to fast-relaxing quadrupolar 14N in amide groups.

PubMed

Chiavazza, Enrico; Kubala, Eugen; Gringeri, Concetta V; Düwel, Stephan; Durst, Markus; Schulte, Rolf F; Menzel, Marion I

2013-02-01

Scalar coupling relaxation, which is usually only associated with closely resonant nuclei (e.g., (79)Br-(13)C), can be a very effective relaxation mechanism. While working on hyperpolarized [5-(13)C]glutamine, fast liquid-state polarization decay during transfer to the MRI scanner was observed. This behavior could hypothetically be explained by substantial T(1) shortening due to a scalar coupling contribution (type II) to the relaxation caused by the fast-relaxing quadrupolar (14)N adjacent to the (13)C nucleus in the amide group. This contribution is only effective in low magnetic fields (i.e., less than 800 μT) and prevents the use of molecules bearing the (13)C-amide group as hyperpolarized MRS/MRI probes. In the present work, this hypothesis is explored both theoretically and experimentally. The results show that high hyperpolarization levels can be retained using either a (15)N-labeled amide or by applying a magnetic field during transfer of the sample from the polarizer to the MRI scanner. Copyright © 2012 Elsevier Inc. All rights reserved.

Ongoing niche differentiation under high gene flow in a polymorphic brackish water threespine stickleback (Gasterosteus aculeatus) population.

PubMed

Østbye, Kjartan; Taugbøl, Annette; Ravinet, Mark; Harrod, Chris; Pettersen, Ruben Alexander; Bernatchez, Louis; Vøllestad, Leif Asbjørn

2018-02-05

Marine threespine sticklebacks colonized and adapted to brackish and freshwater environments since the last Pleistocene glacial. Throughout the Holarctic, three lateral plate morphs are observed; the low, partial and completely plated morph. We test if the three plate morphs in the brackish water Lake Engervann, Norway, differ in body size, trophic morphology (gill raker number and length), niche (stable isotopes; δ 15 N, δ 13 C, and parasites (Theristina gasterostei, Trematoda spp.)), genetic structure (microsatellites) and the lateral-plate encoding Stn382 (Ectodysplasin) gene. We examine differences temporally (autumn 2006/spring 2007) and spatially (upper/lower sections of the lake - reflecting low versus high salinity). All morphs belonged to one gene pool. The complete morph was larger than the low plated, with the partial morph intermediate. The number of lateral plates ranged 8-71, with means of 64.2 for complete, 40.3 for partial, and 14.9 for low plated morph. Stickleback δ 15 N was higher in the lower lake section, while δ 13 C was higher in the upper section. Stickleback isotopic values were greater in autumn. The low plated morph had larger variances in δ 15 N and δ 13 C than the other morphs. Sticklebacks in the upper section had more T. gasterostei than in the lower section which had more Trematoda spp. Sticklebacks had less T. gasterostei, but more Trematoda spp. in autumn than spring. Sticklebacks with few and short rakers had more T. gasterostei, while sticklebacks with longer rakers had more Trematoda. spp. Stickleback with higher δ 15 N values had more T. gasterostei, while sticklebacks with higher δ 15 N and δ 13 C values had more Trematoda spp. The low plated morph had fewer Trematoda spp. than other morphs. Trait-ecology associations may imply that the three lateral plate morphs in the brackish water lagoon of Lake Engervann are experiencing ongoing divergent selection for niche and migratory life history strategies under high gene flow. As such, the brackish water zone may generally act as a generator of genomic diversity to be selected upon in the different environments where threespine sticklebacks can live.

Stable C &N isotopes in 2100 Year-B.P. human bone collagen indicate rare dietary dominance of C4 plants in NE-Italy.

PubMed

Laffranchi, Zita; Huertas, Antonio Delgado; Jiménez Brobeil, Sylvia A; Torres, Arsenio Granados; Riquelme Cantal, Jose A

2016-12-09

C 4 plants (e.g. maize, millet), part of our current diet, are only endemic of reduced areas in South-Europe due to their need of warm climates. Since the first vestiges of agriculture in Europe remains of C 4 plants were recorded but their overall proportion in the human diet remains unknown. Therefore, isotopic (δ 13 C and δ 15 N) composition of bone collagen from the skeletal remains (human and animals) of a Celtic population, Cenomani Gauls, from Verona (3 rd to 1 st century BC) in the NE Italy provide a new perspective on this matter. The δ 13 C collagen values of 90 human skeletal individuals range between -20.2‰ and -9.7‰ (V-PDB) with a mean value of -15.3‰. As present day C 4 plants have δ 13 C values around -11‰, which is equivalent to -9.5‰ for samples of preindustrial age, the less negative δ 13 C values in these individuals indicate a diet dominated by C 4 plants. This palaeodietary study indicates that some European populations predominantly consumed cultivated C 4 plants 2100 year B.P. This is supported by the paleobotanical records and ancient Roman sources (e.g. Pliny the Elder), which indicate that millet was a staple food in South-Europe.

Stable C & N isotopes in 2100 Year-B.P. human bone collagen indicate rare dietary dominance of C4 plants in NE-Italy

NASA Astrophysics Data System (ADS)

Laffranchi, Zita; Huertas, Antonio Delgado; Jiménez Brobeil, Sylvia A.; Torres, Arsenio Granados; Riquelme Cantal, Jose A.

2016-12-01

C4 plants (e.g. maize, millet), part of our current diet, are only endemic of reduced areas in South-Europe due to their need of warm climates. Since the first vestiges of agriculture in Europe remains of C4 plants were recorded but their overall proportion in the human diet remains unknown. Therefore, isotopic (δ13C and δ15N) composition of bone collagen from the skeletal remains (human and animals) of a Celtic population, Cenomani Gauls, from Verona (3rd to 1st century BC) in the NE Italy provide a new perspective on this matter. The δ13C collagen values of 90 human skeletal individuals range between -20.2‰ and -9.7‰ (V-PDB) with a mean value of -15.3‰. As present day C4 plants have δ13C values around -11‰, which is equivalent to -9.5‰ for samples of preindustrial age, the less negative δ13C values in these individuals indicate a diet dominated by C4 plants. This palaeodietary study indicates that some European populations predominantly consumed cultivated C4 plants 2100 year B.P. This is supported by the paleobotanical records and ancient Roman sources (e.g. Pliny the Elder), which indicate that millet was a staple food in South-Europe.

(d ,n ) proton-transfer reactions on 9Be, 11B, 13C, N,1514, and 19F and spectroscopic factors at Ed=16 MeV

NASA Astrophysics Data System (ADS)

Febbraro, M.; Becchetti, F. D.; Torres-Isea, R. O.; Riggins, J.; Lawrence, C. C.; Kolata, J. J.; Howard, A. M.

2017-08-01

The (d ,n ) reaction has been studied with targets of 9Be, 11B, 13C, N,1514, and 19F at Ed=16 MeV using a deuterated liquid-scintillator array. Advanced spectral unfolding techniques with accurately measured scintillator response functions were employed to extract neutron energy spectra without the need for long-path neutron time-of-flight. An analysis of the proton-transfer data at forward angles to the ground states of the final nuclei, using finite-range distorted-wave Born approximation analysis with common bound-state, global, and local optical-model parameter sets, yields a set of self-consistent spectroscopic factors. These are compared with the results of several previous time-of-flight measurements, most done many years ago for individual nuclei at lower energy and often analyzed using zero-range transfer codes. In contrast to some of the earlier published data, our data generally compare well with simple shell-model predictions, with little evidence for uniform quenching (reduction from shell-model values) that has previously been reported from analysis of nucleon knock-out reactions. Data for low-lying excited states in 14N from 13C(d ,n ) also is analyzed and spectroscopic information relevant to nuclear astrophysics obtained. A preliminary study of the radioactive ion beam induced reaction 7Be(d ,n ) , E (7Be)=30 MeV was carried out and indicates further improvements are needed for such measurements, which require detection of neutrons with En<2 MeV .

Distinct Litter Stabilization Dynamics Pathways for Decomposition of Pine Needle and Fine Root Within Soil

NASA Astrophysics Data System (ADS)

Mambelli, S.; Filley, T. R.; Bird, J.; Dawson, T.; Torn, M. S.

2008-12-01

The chemical composition of litter imparts a strong control on the initial rates of microbial decay but it is unclear how plant chemistry influences the ultimate stabilization of soil organic matter (SOM) and the nature of the products stabilized. We determined the concentration and 13C enrichment of lignin phenols and substituted fatty acids (SFA) in SOM fractions from an experiment in which 13C- and 15N-labeled needles or fine roots were added to the mineral soil in a Ponderosa pine (Pinus ponderosa) forest in the Sierra Nevada, CA, USA. 1.5 y after litter addition, we analyzed bulk soil (< 2 mm), free light fraction (LF, mean residence time (MRT) ~5 y) and alkali/acid insoluble humin (MRT ~270 y) fractions. Needles contained nearly 2 and 3x the lignin and SFA content per organic carbon unit as did roots. Lignin and SFA decreased from the free LF to the bulk soil to the humin fraction; and molecular properties were more similar within a SOM fraction regardless of the litter source. However, LF and humin from the root addition contained more lignin than from the needle addition. Based upon the relative movement of litter-derived 13C and 15N into SOM fractions during 1.5 y, it was proposed that the 13C accumulation in the humin fraction for needles was derived from high C/N, needle-derived biopolymer molecular fragments that are surficially associated with particles. In contrast, the root-derived material entering SOM fractions was much lower in C/N and was likely from microbial by-products. Consistent with this hypothesis, both lignin and SFA in the LF and humin fractions amended with enriched needles were highly enriched (+ 30-60 permil) with respect to the SOM fractions from soils amended with roots. These differences were large even considering the lower concentration of SFA and lignin in root material. Although the chemistry and MRT of LF and humin were dramatically different, the extent of 13C-enrichment among lignin and SFA were comparable for the needle experiment while most lignin phenols for the humin from the root addition had greater 13C content than SFA. This indicates that molecular fragments of plant biopolymers can readily associate with both labile and stabilized SOM fractions. At the same time, these results suggest that distinct decomposition and stabilization pathways exist for litters, such as needles vs. roots, of different chemical quality.

Effective rotational correlation times of proteins from NMR relaxation interference

NASA Astrophysics Data System (ADS)

Lee, Donghan; Hilty, Christian; Wider, Gerhard; Wüthrich, Kurt

2006-01-01

Knowledge of the effective rotational correlation times, τc, for the modulation of anisotropic spin-spin interactions in macromolecules subject to Brownian motion in solution is of key interest for the practice of NMR spectroscopy in structural biology. The value of τc enables an estimate of the NMR spin relaxation rates, and indicates possible aggregation of the macromolecular species. This paper reports a novel NMR pulse scheme, [ 15N, 1H]-TRACT, which is based on transverse relaxation-optimized spectroscopy and permits to determine τc for 15N- 1H bonds without interference from dipole-dipole coupling of the amide proton with remote protons. [ 15N, 1H]-TRACT is highly efficient since only a series of one-dimensional NMR spectra need to be recorded. Its use is suggested for a quick estimate of the rotational correlation time, to monitor sample quality and to determine optimal parameters for complex multidimensional NMR experiments. Practical applications are illustrated with the 110 kDa 7,8-dihydroneopterin aldolase from Staphylococcus aureus, the uniformly 15N-labeled Escherichia coli outer membrane protein X (OmpX) in 60 kDa mixed OmpX/DHPC micelles with approximately 90 molecules of unlabeled 1,2-dihexanoyl- sn-glycero-3-phosphocholine (DHPC), and the 16 kDa pheromone-binding protein from Bombyx mori, which cover a wide range of correlation times.

Schottky barrier detection devices having a 4H-SiC n-type epitaxial layer

DOEpatents

Mandal, Krishna C.; Terry, J. Russell

2016-12-06

A detection device, along with methods of its manufacture and use, is provided. The detection device can include: a SiC substrate defining a substrate surface cut from planar to about 12.degree.; a buffer epitaxial layer on the substrate surface; a n-type epitaxial layer on the buffer epitaxial layer; and a top contact on the n-type epitaxial layer. The buffer epitaxial layer can include a n-type 4H--SiC epitaxial layer doped at a concentration of about 1.times.10.sup.15 cm.sup.-3 to about 5.times.10.sup.18 cm.sup.-3 with nitrogen, boron, aluminum, or a mixture thereof. The n-type epitaxial layer can include a n-type 4H--SiC epitaxial layer doped at a concentration of about 1.times.10.sup.13 cm.sup.-3 to about 5.times.10.sup.15 cm.sup.-3 with nitrogen. The top contact can have a thickness of about 8 nm to about 15 nm.

Carbon and nitrogen stable isotope ratios of pelagic zooplankton elucidate ecohydrographic features in the oligotrophic Red Sea

NASA Astrophysics Data System (ADS)

Kürten, Benjamin; Al-Aidaroos, Ali M.; Kürten, Saskia; El-Sherbiny, Mohsen M.; Devassy, Reny P.; Struck, Ulrich; Zarokanellos, Nikolaos; Jones, Burton H.; Hansen, Thomas; Bruss, Gerd; Sommer, Ulrich

2016-01-01

Although zooplankton occupy key roles in aquatic biogeochemical cycles, little is known about the pelagic food web and trophodynamics of zooplankton in the Red Sea. Natural abundance stable isotope analysis (SIA) of carbon (δ13C) and N (δ15N) is one approach to elucidating pelagic food web structures and diet assimilation. Integrating the combined effects of ecological processes and hydrography, ecohydrographic features often translate into geographic patterns in δ13C and δ15N values at the base of food webs. This is due, for example, to divergent 15N abundances in source end-members (deep water sources: high δ15N, diazotrophs: low δ15N). Such patterns in the spatial distributions of stable isotope values were coined isoscapes. Empirical data of atmospheric, oceanographic, and biological processes, which drive the ecohydrographic gradients of the oligotrophic Red Sea, are under-explored and some rather anticipated than proven. Specifically, five processes underpin Red Sea gradients: (a) monsoon-related intrusions of nutrient-rich Indian Ocean water; (b) basin scale thermohaline circulation; (c) mesoscale eddy activity that causes up-welling of deep water nutrients into the upper layer; (d) the biological fixation of atmospheric nitrogen (N2) by diazotrophs; and (e) the deposition of dust and aerosol-derived N. This study assessed relationships between environmental samples (nutrients, chlorophyll a), oceanographic data (temperature, salinity, current velocity [ADCP]), particulate organic matter (POM), and net-phytoplankton, with the δ13C and δ15N values of zooplankton collected in spring 2012 from 16°28‧ to 26°57‧N along the central axis of the Red Sea. The δ15N of bulk POM and most zooplankton taxa increased from North (Duba) to South (Farasan). The potential contribution of deep water nutrient-fueled phytoplankton, POM, and diazotrophs varied among sites. Estimates suggested higher diazotroph contributions in the North, a greater contribution of POM in the South, and of small phytoplankton in the central Red Sea. Consistent variation across taxonomic and trophic groups at latitudinal scale, corresponding with patterns of nutrient stoichiometry and phytoplankton composition, indicates that the zooplankton ecology in the Red Sea is largely influenced by hydrographic features. It suggests that the primary ecohydrography of the Red Sea is driven not only by the thermohaline circulation, but also by mesoscale activities that transports nutrients to the upper water layers and interact with the general circulation pattern. Ecohydrographic features of the Red Sea, therefore, aid in explaining the observed configuration of its isoscape at the macroecological scale.

1H, 13C and 15N assignment of the C-terminal domain of GNA2132 from Neisseria meningitidis.

PubMed

Esposito, Veronica; Musi, Valeria; Veggi, Daniele; Pastore, Annalisa; Pizza, Mariagrazia

2010-04-01

GNA2132 (Genome-derived Neisseria Antigen 2132) is a surface-exposed lipoprotein discovered by reverse vaccinology and expressed by genetically diverse Neisseria meningitidis strains (Pizza et al. 2000). The protein induces bactericidal antibodies against most strains of Meningococccus and has been included in a multivalent recombinant vaccine against N. meningitidis serogroup B. Structure determination of GNA2132 is important for understanding the antigenic properties of the protein in view of increased efficiency vaccine development. We report practically complete (1)H, (13)C and (15)N assignment of the detectable spectrum of a highly conserved C-terminal region of GNA2132 (residues 245-427) in micellar solution, a medium used to improve the spectral quality. The first 32 residues of our construct up to residue 277 were not visible in the spectrum, presumably because of line broadening due to solvent and/or conformational exchange. Secondary structure predictions based on chemical shift information indicate the presence of an all beta-protein with eight beta strands.

The isotropic condition of energetic particles emitted from a large solar flare. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Spalding, J.

1983-01-01

Isotope abundance ratios for 5 to 50 MeV/nuc nuclei from a large solar flare were measured. The measurements were made by the heavy isotope spectrometer telescope (HIST) on the ISEE-3 satellite orbiting the Sun near an Earth-Sun liberation point approximately one million miles sunward of the Earth. Finite values for the isotope abundance ratios C-13/C-12, N-15/N-14, O-18/O-16, Ne-22/Ne-20, Mg-25/Mg-24, and Mg-26/Mg-24, and upper limits for the isotope abundance ratios He-3/He-4, C-14/C-12, O-17/O-16 and Ne-21/Ne-20 were reported. Element abundances and spectra were measured to compare the flare with other reported flares. The flare is a typical large flare with low Fe/O abundance or = to 0.1). For C-13/C-12, N-15/N-14, O-18/O-16, Mg-25/Mg-24 and Mg-26/Mg-24 isotope abundance ratios agree with the solar system abundance ratios. Measurement for Ne-22/Ne-20 agree with the isotopic composition of the meteoritic component neon-A.

Structures of Highly Twisted Amides Relevant to Amide N-C Cross-Coupling: Evidence for Ground-State Amide Destabilization.

PubMed

Pace, Vittorio; Holzer, Wolfgang; Meng, Guangrong; Shi, Shicheng; Lalancette, Roger; Szostak, Roman; Szostak, Michal

2016-10-04

Herein, we show that acyclic amides that have recently enabled a series of elusive transition-metal-catalyzed N-C activation/cross-coupling reactions are highly twisted around the N-C(O) axis by a new destabilization mechanism of the amide bond. A unique effect of the N-glutarimide substituent, leading to uniformly high twist (ca. 90°) irrespective of the steric effect at the carbon side of the amide bond has been found. This represents the first example of a twisted amide that does not bear significant steric hindrance at the α-carbon atom. The (15) N NMR data show linear correlations between electron density at nitrogen and amide bond twist. This study strongly supports the concept of amide bond ground-state twist as a blueprint for activation of amides toward N-C bond cleavage. The new mechanism offers considerable opportunities for organic synthesis and biological processes involving non-planar amide bonds. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Stable isotope analysis of food-web system in subarctic to subtropical region of western North Pacific

NASA Astrophysics Data System (ADS)

Aita, M. N.; Minoru, K.; Kobari, T.; Yoshikawa, C.; Ishii, R.

2016-02-01

Carbon and nitrogen isotope ratios of biota are controlled by two factors, a metabolic system and a lifestyle of predator and a regional variability of environmental parameters on food web system. To evaluate the environmental factors (i.e., nutrients and temperature) on the basic food web in the marine ecosystem. We studied the seasonal variation of nitrogen and carbon isotope ratios of zooplankton in the subarctic site of K2 (47ºN, 160ºE) and the subtropical one of S1 (30ºN, 145ºE) in the western North Pacific Ocean, both of which are JAMSTEC observation site. Biota were collected in eight depths (0-50, 50-100, 100-150, 150-200, 200-300, 300-500, 500-750, 750-1000m) at both sites using IONESS from February 2010 to July 2011. All samples were classified under a stereomicroscope into species or genus level and used adult stage for isotopic analysis. We also collected water samples from seasonal and vertical (from the surface to 1,000m depth) profiles in δ15N (NO3+ + NO2-) at K2 and S1 in special reference to nitrogen cycles. The δ15N and δ13C values of amphipods and copepod, omnivorous zooplankton in the surface ocean, showed a large seasonal variation. The δ15N values of zooplankton and nitrate ions in the water at the S1 site tended to be lower than those at the K2 site, indicating that the basic food web could be affected by nitrogen fixation. We further compared the trophic fractionation of carbon and nitrogen isotopes (Δδ13C, Δδ15N). It was observed that a simple relationship exists in the Δδ15N/Δδ13C regardless of species and ecosystems. This contention suggests a unified regularity is maintained in the lower to higher trophic level in the marine ecosystem.

High-resolution Records of Proteinaceous Deep-Sea Coral δ13C and δ15N Values in the North Pacific Subtropical Gyre Suggest Major Shifts in Nutrient and Phytoplankton Dynamics over the last 5000 years

NASA Astrophysics Data System (ADS)

Glynn, D. S.; McCarthy, M. D.; McMahon, K.; Guilderson, T. P.

2016-02-01

The North Pacific Subtropical Gyre (NPSG) is the largest continuous ecosystem on this planet, and currently expanding in a warming global climate. To understand current and future dynamics in productivity, biogeochemical cycling, and carbon sequestration, we must develop a more complete understanding of the dynamics in this important ecosystem in the past. Low sedimentation rates and high bioturbation make ocean-open sediment cores difficult to interpret at sufficiently high resolution. In contrast, deep-sea corals act as `living sediment traps' and incorporate the signal of sinking organic matter directly into the chronological growth bands of their proteinaceous skeletons. We reconstructed a 5,000 year, high resolution (decadal-scale) record of past changes in stable bulk nitrogen (δ15N) and carbon isotopes (δ13C) from multiple deep-sea corals around the Hawaiian archipelago. Previous studies have indicated a substantial decrease in both δ15N and δ13C (1 to 1.5‰) since the onset of the Industrial Revolution ( 1850s) to 1,000 year lows of 8‰ and -17‰ respectively (Sherwood et al. 2014, McMahon et al. 2015). Our new data now reveals that shifts of this magnitude are not unprecedented in the Mid- to Late Holocene. Our extended record indicates that over multi-millennial time scales there is a large range of natural variability, with δ15N values ranging from 8‰ to 12‰ and δ13C values ranging from -17‰ to -15‰. We propose that these signals reflect primarily shifts in phytoplankton species composition (as indicated by previous compound-specific work with amino acids). Comparisons with climate records suggest that these shifts may be directly linked to past changes in temperature (ocean stratification) and dust inputs. This study represents the first high-resolution record of nutrient and ecosystem dynamics in the NPSG over the past five millennia, and offers a historical baseline to better analyze the effects of current and future anthropogenic climate forcing.