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Sample records for isotope dual-labelling approach

  1. Dual Label Stable Isotope Incubations Followed By Single Cell Nanosims Analyses To Investigate Microscale Phototroph-Heterotroph Interactions

    NASA Astrophysics Data System (ADS)

    Mayali, X.; Samo, T. J.; Nilson, D.; Arandia Gorostidi, N.; alonso Saez, L.; Moran, X. A.; Weber, P. K.

    2015-12-01

    In natural ecosystems such as lakes and oceans as well as human-engineered systems for sunlight-regulated biomass production (such as algal biofuel ponds), the interaction between autotrophic and heterotrophic processes are critical to determine whether such systems are net autotrophic or heterotrophic. Traditional methods to quantify autotrophy and heterotrophy include primary productivity and bacterial production measurements using radiolabeled substrates that quantify these processes on the bulk scale. To examine the microscale interactions between individual autotrophic and heterotrophic cells, we incubate mixed microbial assemblages with 13C-bicarbonate and 15N-leucine to label individual autotrophs and heterotrophs, respectively. We use nano imaging secondary ion mass spectrometry (with a Cameca NanoSIMS 50) to quantify the incorporation of the rare isotopes by single cells. We will present results from experiments examining the impact of warming on the exchange of C and N between algal and bacterial cells from the coastal Atlantic Ocean, which suggest that increased temperature may strengthen physical interactions and exchange. We will also present data from experiments examining the influence of attached bacteria on the cell-specific inorganic carbon fixation rates of biofuel-producing algal cultures which suggest that certain algal-attached bacterial groups grow faster than when free-living and influence algal growth. We conclude that the examination of individual cells uncover interactions that would be difficult, if not impossible, to investigate with bulk methods.

  2. Antibody and DNA dual-labeled gold nanoparticles: Stability and reactivity

    NASA Astrophysics Data System (ADS)

    Qiao, Fei-Yan; Liu, Jun; Li, Fu-Rong; Kong, Xiao-Li; Zhang, Hao-Li; Zhou, Han-Xin

    2008-03-01

    Gold nanoparticles labeled by both antibody (IgG) and single stranded DNA (ss-DNA) have been synthesized and characterized. The stability and reactivity of the dual-labeled nanoparticles were compared with the conventional IgG or ss-DNA modified nanoparticles. It was found that the IgG adsorption significantly improved the stability of the nanoparticles in aqueous solution, which is beneficial for attaching ss-DNA. The presence of IgG also effectively prohibits the desorption of ss-DNA against dithiothreitol (DTT) displacement. The coverage on dual-labeled nanoparticles was found to be 50 ± 15 ss-DNA/nanoparticle and 10 ± 2 IgG/nanoparticle, respectively, compared to the value of 70 ± 15 ss-DNA/nanoparticle of only ss-DNA-labeled gold nanoparticles. Dot-immuno and cross-linking experiments confirmed that both the IgG and ss-DNA retained their bioactivity on the nanoparticle surface. The dual-labeled nanoparticles have potential to be used as novel bio-probes for ultrasensitive detection.

  3. Radioassay of dual-labeled samples with a Cherenkov counting technique

    NASA Astrophysics Data System (ADS)

    Fujii, Haruo; Takiue, Makoto

    1998-03-01

    A new Cherenkov counting technique which allows radioactivities of a dual-labeled sample to be determined simultaneously by using a wavelength shifter has been proposed, and tested for the pairs 32P-36Cl and 86Rb-36Cl. The minimum requirements for this method are a single channel liquid scintillation counter, a wavelength shifter and a reference sample for determining the Cherenkov counting efficiency. The simple procedure for sample preparation and measurement makes the technique very useful for routine radioassay with the help of a desk-top computer.

  4. Radioassay of dual-labeled samples with a Cherenkov counting technique

    NASA Astrophysics Data System (ADS)

    Fujii, Haruo; Takiue, Makoto

    1988-03-01

    A new Cherenkov counting technique which allows radioactivities of a dual-labeled sample to be determined simultaneously by using a wavelength shifter has been proposed, and tested for the pairs 32P 36Cl and 86Rb 36Cl. The minimum requirements for this method are a single channel liquid scintillation counter, a wavelength shifter and a reference sample for determining the Cherenkov counting efficiency. The simple procedure for sample preparation and measurement makes the technique very useful for routine radioassay with the help of a desk-top computer.

  5. Nuclear and optical dual-labelled imaging agents. Design and challenges.

    PubMed

    Singh, G; Gott, M D; Pietzsch, H-J; Stephan, H

    2016-04-12

    Over the last two decades, molecular imaging has been established as a valuable technology, aiming at visualization and characterization of biochemical processes on a molecular level in isolated cells, tissues and higher organisms. Within the wide scope of the various imaging techniques, dual-labelled modalities for nuclear (PET, SPECT) and near-infrared fluorescence (NIRF) imaging show promise owing to their comparable detection sensitivity. Novel materials offer excellent prospects for the development of new non-invasive strategies of early diagnosis and efficient monitoring of therapeutic treatments. In the field of cancer medicine, the combination of different imaging techniques such as PET/SPECT and OI for tracking down tumours and metastases, and subsequent image-guided surgery for tumour resection is particularly attractive. This review focuses on the development of promising dual-labelled agents to be applied in bimodal nuclear/optical imaging, combining radionuclides and fluorescent dyes. The discussion encompasses modular ligands as well as nanoscale systems, including antibodies and their fragments. PMID:27067792

  6. Simultaneous detection of imidacloprid and parathion by the dual-labeled time-resolved fluoroimmunoassay.

    PubMed

    Shi, Haiyan; Sheng, Enze; Feng, Lu; Zhou, Liangliang; Hua, Xiude; Wang, Minghua

    2015-10-01

    A highly sensitive direct dual-labeled time-resolved fluoroimmunoassay (TRFIA) to detect parathion and imidacloprid simultaneously in food and environmental matrices was developed. Europium (Eu(3+)) and samarium (Sm(3+)) were used as fluorescent labels by coupling separately with L1-Ab and A1P1-Ab. Under optimal assay conditions, the half-maximal inhibition concentration (IC50) and limit of detection (LOD, IC10) were 10.87 and 0.025 μg/L for parathion and 7.08 and 0.028 μg/L for imidacloprid, respectively. The cross-reactivities (CR) were negligible except for methyl-parathion (42.4 %) and imidaclothiz (103.4 %). The average recoveries of imidacloprid ranged from 78.9 to 104.2 % in water, soil, rice, tomato, and Chinese cabbage with a relative standard deviation (RSD) of 2.4 to 11.6 %, and those of parathion were from 81.5 to 110.9 % with the RSD of 3.2 to 10.5 %. The results of TRFIA for the authentic samples were validated by comparison with gas chromatography (GC) analyses, and satisfactory correlations (parathion: R (2) = 0.9918; imidacloprid: R (2) = 0.9908) were obtained. The results indicate that the dual-labeled TRFIA is convenient and reliable to detect parathion and imidacloprid simultaneously in food and environmental matrices. PMID:25994268

  7. Solid- and solution-phase synthesis and application of R6G dual-labeled oligonucleotide probes.

    PubMed

    Skoblov, Aleksander Yu; Vichuzhanin, Maxim V; Farzan, Valentina M; Veselova, Olga A; Konovalova, Tatiana A; Podkolzin, Alexander T; Shipulin, German A; Zatsepin, Timofei S

    2015-10-15

    A novel N-TFA-protected carboxyrhodamine 6G (R6G) phosphoramidite was synthesized for use in an automated DNA synthesis to prepare 5'-labeled oligonucleotides. Deprotection and purification conditions were optimized for 5'-labeled and dual-labeled oligonucleotide probes. As an alternative we synthesized an azide derivative of R6G for CuAAC post-synthetic oligonucleotide labeling. Dual-labeled probes obtained by both methods showed the same efficacy in a quantitative PCR assay. R6G-labeled probes demonstrated superior properties in a qPCR assay in comparison with alternative HEX, JOE and SIMA dyes due to more efficient fluorescence quenching by BHQ-1. We successfully used R6G dual-labeled probes for rotavirus genotyping. PMID:26392371

  8. New approaches to the Moon's isotopic crisis

    PubMed Central

    Melosh, H. J.

    2014-01-01

    Recent comparisons of the isotopic compositions of the Earth and the Moon show that, unlike nearly every other body known in the Solar System, our satellite's isotopic ratios are nearly identical to the Earth's for nearly every isotopic system. The Moon's chemical make-up, however, differs from the Earth's in its low volatile content and perhaps in the elevated abundance of oxidized iron. This surprising situation is not readily explained by current impact models of the Moon's origin and offers a major clue to the Moon's formation, if we only could understand it properly. Current ideas to explain this similarity range from assuming an impactor with the same isotopic composition as the Earth to postulating a pure ice impactor that completely vaporized upon impact. Several recent proposals follow from the suggestion that the Earth–Moon system may have lost a great deal of angular momentum during early resonant interactions. The isotopic constraint may be the most stringent test yet for theories of the Moon's origin. PMID:25114301

  9. New approaches to the Moon's isotopic crisis.

    PubMed

    Melosh, H J

    2014-09-13

    Recent comparisons of the isotopic compositions of the Earth and the Moon show that, unlike nearly every other body known in the Solar System, our satellite's isotopic ratios are nearly identical to the Earth's for nearly every isotopic system. The Moon's chemical make-up, however, differs from the Earth's in its low volatile content and perhaps in the elevated abundance of oxidized iron. This surprising situation is not readily explained by current impact models of the Moon's origin and offers a major clue to the Moon's formation, if we only could understand it properly. Current ideas to explain this similarity range from assuming an impactor with the same isotopic composition as the Earth to postulating a pure ice impactor that completely vaporized upon impact. Several recent proposals follow from the suggestion that the Earth-Moon system may have lost a great deal of angular momentum during early resonant interactions. The isotopic constraint may be the most stringent test yet for theories of the Moon's origin. PMID:25114301

  10. Simultaneous detection of sulfamethazine and sulfaquinoxaline using a dual-label time-resolved fluorescence immunoassay.

    PubMed

    Le, Tao; Yan, Peifeng; Liu, Jin; Wei, Shu

    2013-01-01

    A dual-label time-resolved fluoroimmunoassay (TRFIA) was introduced for the simultaneous quantification of sulfamethazine (SM2) and sulfaquinoxaline (SQX). Lanthanide (Eu(3+) and Sm(3+))-labelled antibodies were used because lanthanides have higher stabilities and narrower emission spectra than most fluorescent dyes. The sensitivity of the TRFIA for SM2 was 0.02 ng ml(-1), and the average recoveries and the intra- and inter-assay CVs were 77.2-107.6%, 5.4-10.5%, and 6.0-11.2%, respectively. The sensitivity of the TRFIA for SQX was 0.04 ng ml(-1); and the average recoveries and the intra- and inter-assay CVs were 74.1-102.8%, 4.6-10.9%, and 8.7-11.2%, respectively. The method was used to analyse chicken tissue and egg samples, and the results agreed well with the results of HPLC and enzyme-linked immunosorbent assay (ELISA) analyses, with correlation coefficients (R(2)) of 0.9415-0.9724. The TRFIA developed is a simple, fast and sensitive method for the high-throughput simultaneous screening of SM2 and SQX in edible animal tissues. PMID:23782396

  11. New approaches to paleothermometry from isotopes in precipitation

    NASA Astrophysics Data System (ADS)

    Steig, E. J.

    2015-12-01

    Water isotope ratios in precipitation have been used as paleothermometers for at least 50 years. Most temperature reconstructions using isotope ratios rely on the empirical observation of a correlation between isotope ratios and temperature. While this approach is supported by theoretical considerations, it is nevertheless inherently imprecise because the correlation arises from myriad processes in the atmosphere that cannot be direclty quantified. In this talk, I will discuss two major innovations in the use of isotope ratios to obtain paleotemperature from ice cores. First, the measurement of very high resolution isotope records allows for the determination of the diffusion length (the amount of isotope diffusion that has occurred), which is strongly dependent on temperature. Second, the novel measurement of the third naturally occuring isotope of oxygen -- oxygen 17 -- allows the measurement of the oxygen-17 excess, which provides new constraints temperature because it depends strongly on the temperature-dependent supersaturation. Both these approaches have a stronger theoretical foundation than the tradiational δ18O method, and have the potential to be both more accurate and precise.

  12. Radiogenic isotopic approaches for quantifying radionuclide transport (Invited)

    NASA Astrophysics Data System (ADS)

    Maher, K.; Depaolo, D. J.; Singleton, M. J.; Christensen, J. N.; Conrad, M. E.

    2009-12-01

    Naturally occurring variations in the isotopic compositions of U and Sr provide unique opportunities for assessing the fate and transport of radionuclides at field-scale conditions. When coupled with reactive transport models, U and Sr isotopes may also provide additional constraints on the rates of sediment-fluid or sediment-waste interactions. Such isotopic approaches can be useful for sites where subsurface characterization is complicated by a lack of accessibility or the presence of substantial heterogeneity. In addition, a variety of quantitative modeling approaches of different complexity can be used to evaluate experimentally determined parameters for radionuclide mobility at the field-scale. At the Hanford Site in eastern Washington, 87Sr/86Sr and 234U/238U ratios have been used to quantify the residence time of Sr and U in the unsaturated zone, the long-term background infiltration rate through the unsaturated zone, and to assess the influence of enhanced wastewater discharge on the regional unconfined aquifer. As a result of different processing techniques or due to interactions between caustic waste and the natural sediment, waste plumes may also inherit isotopic fingerprints (e.g. 234U/238U, 235U/238U, 236U/238U; δ15N & δ18O of nitrate) that can be used to resolve multiple sources of contamination. Finally, enriched isotopic tracers can be applied to experimental manipulations to assess the retardation of a variety of contaminants. Collectively this isotopic data contributes unique perspectives on both the hydrologic conditions across the site and the mobility of key radionuclides. Predicting the long-term fate and transport of radionuclides in the environment is often challenging due to natural heterogeneity and incomplete characterization of the subsurface, however detailed analysis of isotopic variations can provide one additional means of characterizing the subsurface.

  13. Dual-labeled time-resolved fluoroimmunoassay for simultaneous detection of clothianidin and diniconazole in agricultural samples.

    PubMed

    Sheng, Enze; Shi, Haiyan; Zhou, Liangliang; Hua, Xiude; Feng, Lu; Yu, Tong; Wang, Minghua

    2016-02-01

    Europium (Eu(3+)) and samarium (Sm(3+)) were used as fluorescent labels to develop a highly sensitive dual-labeled time-resolved fluoroimmunoassay (TRFIA) for detect clothianidin and diniconazole in food samples. Under the optimized assay conditions, 50% inhibition concentration (IC50) and the limit of detection (LOD, IC10) of clothianidin were 5.08 and 0.021 μg/L, and 13.14 and 0.029 μg/L for diniconazole. The cross-reactivities (CRs) were negligible except dinotefuran (9.4%) and uniconazole (4.28%). The recoveries of clothianidin and diniconazole ranged from 79.3% to 108.7% in food samples. The results of TRFIA for the authentic samples were validated by gas chromatography (GC) analyses, and a satisfactory correlations were obtained. These results indicated that the method was an alternative tool for simultaneous detection of clothianidin and diniconazole in food samples. PMID:26304380

  14. Dual-label quantum dot-based immunoassay for simultaneous determination of Carbadox and Olaquindox metabolites in animal tissues.

    PubMed

    Le, Tao; Zhu, Liqian; Yu, Huan

    2016-05-15

    A novel and reliable dual-label direct competitive fluorescence-linked immunosorbent assay (dc-FLISA) based on quantum dots (QDs) was developed for the simultaneous determination of the major metabolites of Carbadox and Olaquindox residues in animal tissues, using anti-QCA monoclonal antibodies and anti-MQCA polyclonal antibodies labeled with QD520 and QD635, respectively. The limits of detection for QCA and MQCA were 0.05 and 0.07ng/ml, respectively. The method was used to analyze fortified samples and analyte recoveries ranged from 81.5% to 98.2% (QCA) and 84.2% to 95.7% (MQCA). Good correlations between the dc-FLISA method and HPLC were demonstrated for the determination of QCA and MQCA residues in swine tissue samples, confirming the reliability of the proposed method. PMID:26775945

  15. Positron Emission Tomography and Optical Imaging of Tumor CD105 Expression with a Dual-Labeled Monoclonal Antibody

    PubMed Central

    Zhang, Yin; Hong, Hao; Engle, Jonathan W.; Yang, Yunan; Theuer, Charles P.; Barnhart, Todd E.; Cai, Weibo

    2012-01-01

    CD105 (endoglin) is an independent prognostic marker for poor prognosis in > 10 solid tumor types, including breast cancer. The goal of this study was to develop a CD105-specific agent for both positron emission tomography (PET) and near-infrared fluorescence (NIRF) imaging, which can have potential clinical applications in diagnosis and imaged-guided surgery of breast cancer. TRC105, a chimeric anti-CD105 monoclonal antibody, was labeled with both a NIRF dye (i.e. 800CW) and 64Cu to yield 64Cu-NOTA-TRC105-800CW. Flow cytometry analysis revealed no difference in CD105 binding affinity/specificity between TRC105 and NOTA-TRC105-800CW. Serial PET imaging revealed that the 4T1 murine breast tumor uptake of 64Cu-NOTA-TRC105-800CW was 5.2 ± 2.7, 11.0 ± 1.4, and 13.0 ± 0.4 %ID/g at 4, 24, and 48 h post-injection respectively. Tumor uptake as measured by ex vivo NIRF imaging exhibited a good linear correlation with the %ID/g values obtained from PET (R = 0.74). Biodistribution data were consistent with the PET/NIRF findings. Blocking experiments, control studies with dual-labeled cetuximab (an isotype-matched control antibody), and histology confirmed the CD105 specificity of 64Cu-NOTA-TRC105-800CW. Successful PET/NIRF imaging of CD105 expression warrants further investigation and clinical translation of dual-labeled TRC105-based imaging agents. PMID:22292418

  16. Positron emission tomography and optical imaging of tumor CD105 expression with a dual-labeled monoclonal antibody.

    PubMed

    Zhang, Yin; Hong, Hao; Engle, Jonathan W; Yang, Yunan; Theuer, Charles P; Barnhart, Todd E; Cai, Weibo

    2012-03-01

    CD105 (endoglin) is an independent prognostic marker for poor prognosis in >10 solid tumor types, including breast cancer. The goal of this study was to develop a CD105-specific agent for both positron emission tomography (PET) and near-infrared fluorescence (NIRF) imaging, which can have potential clinical applications in diagnosis and imaged-guided surgery of breast cancer. TRC105, a chimeric anti-CD105 monoclonal antibody, was labeled with both a NIRF dye (i.e., 800CW) and (64)Cu to yield (64)Cu-NOTA-TRC105-800CW. Flow cytometry analysis revealed no difference in CD105 binding affinity/specificity between TRC105 and NOTA-TRC105-800CW. Serial PET imaging revealed that the 4T1 murine breast tumor uptake of (64)Cu-NOTA-TRC105-800CW was 5.2 ± 2.7, 11.0 ± 1.4, and 13.0 ± 0.4% ID/g at 4, 24, and 48 h postinjection respectively. Tumor uptake as measured by ex vivo NIRF imaging exhibited a good linear correlation with the % ID/g values obtained from PET (R = 0.74). Biodistribution data were consistent with the PET/NIRF findings. Blocking experiments, control studies with dual-labeled cetuximab (an isotype-matched control antibody), and histology confirmed the CD105 specificity of (64)Cu-NOTA-TRC105-800CW. Successful PET/NIRF imaging of CD105 expression warrants further investigation and clinical translation of dual-labeled TRC105-based imaging agents. PMID:22292418

  17. Influence of chelator and near-infrared dye labeling on biocharacteristics of dual-labeled trastuzumab-based imaging agents

    PubMed Central

    Aldrich, Melissa B; Yang, Zhi; Zhou, Nina; Xie, Qing; Liu, Chen; Sevick-Muraca, Eva

    2016-01-01

    Objective To investigate the effect of fluorescent dye labeling on the targeting capabilities of 111In- (DTPA)n-trastuzumab-(IRDye 800)m. Methods Trastuzumab-based conjugates were synthesized and conjugated with diethylenetriaminepentaacetic acid (DTPA) at molar ratios of 1, 2, 3 and 5 and with a fluorescent dye (IRDye 800CW) at molar ratios of 1, 3 and 5. Immunoreactivity and internalization were assessed on SKBR-3 cells, overexpressing human epidermal growth factor receptor 2. The stability in human serum and phosphate-buffered saline (PBS) was evaluated. The biodistribution of dual-labeled conjugates was compared with that of 111In-(DTPA)2-trastuzumab in a SKBR-3 xenograft model to evaluate the effect of dye-to-protein ratio. Results All trastuzumab-based conjugates exhibited a high level of chemical and optical purity. Flow cytometry results showed that increasing dye-to-protein ratios were associated with decreased immunoreactivity. Stability studies revealed that the conjugate was stable in PBS, while in human serum, increased degradation and protein precipitation were observed with increasing dye-to-protein ratios. At 4 h, the percentages of internalization of dual-labeled conjugates normalized by dye-to-protein ratio (m) were 24.88%±2.10%, 19.99%±0.59%, and 17.47%±1.26% for "m" equal to 1, 3, and 5, respectively. A biodistribution study revealed a progressive decrease in tumor uptake with an increase in the dye-to-protein ratios. The liver, spleen and kidney showed a marked uptake with increased dye-to-protein ratios, particularly in the latter. Conclusions With non-specific-site conjugation of the fluorescent dye with a protein based on imaging agent, the increase in dye-to-protein ratios negatively impacted the immunoreactivity and stability, indicating a reduced tumor uptake. PMID:27478322

  18. Nitrate in groundwater: an isotopic multi-tracer approach

    NASA Astrophysics Data System (ADS)

    Widory, David; Kloppmann, Wolfram; Chery, Laurence; Bonnin, Jacky; Rochdi, Houda; Guinamant, Jean-Luc

    2004-08-01

    In spite of increasing efforts to reduce nitrogen inputs into groundwater from intensive agriculture, nitrate (NO 3) remains one of the major pollutants of drinking-water resources worldwide. Determining the source(s) of NO 3 contamination in groundwater is an important first step for improving groundwater quality by emission control, and it is with this aim that we investigated the viability of an isotopic multi-tracer approach ( δ15N, δ11B, 87Sr/ 86Sr), in addition to conventional hydrogeologic analysis, in two small catchments of the Arguenon watershed (Brittany, France). The main anthropogenic sources (fertilizer, sewage effluent, and hog, cattle and poultry manure) were first characterized by their specific B, N and Sr isotope signatures, and compared to those observed in the ground- and surface waters. Chemical and isotopic evidence shows that both denitrification and mixing within the watershed have the effect of buffering NO 3 contamination in the groundwater. Coupled δ11B, δ15N and 87Sr/ 86Sr results indicate that a large part of the NO 3 contamination in the Arguenon watershed originates from the spreading of animal manure, with hog manure being a major contributor. Point sources, such as sewage effluents, contribute to the NO 3 budget of the two watersheds.

  19. Comparative Evaluation of Sloppy Molecular Beacon and Dual-Labeled Probe Melting Temperature Assays to Identify Mutations in Mycobacterium tuberculosis Resulting in Rifampin, Fluoroquinolone and Aminoglycoside Resistance.

    PubMed

    Roh, Sandy S; Smith, Laura E; Lee, Jong Seok; Via, Laura E; Barry, Clifton E; Alland, David; Chakravorty, Soumitesh

    2015-01-01

    Several molecular assays to detect resistance to Rifampin, the Fluoroquinolones, and Aminoglycosides in Mycobacterium tuberculosis (M. tuberculosis) have been recently described. A systematic approach for comparing these assays in the laboratory is needed in order to determine the relative advantage of each assay and to decide which ones should be advanced to evaluation. We performed an analytic comparison of a Sloppy Molecular Beacon (SMB) melting temperature (Tm) assay and a Dual labeled probe (DLP) Tm assay. Both assays targeted the M. tuberculosis rpoB, gyrA, rrs genes and the eis promoter region. The sensitivity and specificity to detect mutations, analytic limit of detection (LOD) and the detection of heteroresistance were tested using a panel of 56 clinical DNA samples from drug resistant M. tuberculosis strains. Both SMB and DLP assays detected 29/29 (100%) samples with rpoB RRDR mutations and 3/3 (100%) samples with eis promoter mutations correctly. The SMB assay detected all 17/17 gyrA mutants and 22/22 rrs mutants, while the DLP assay detected 16/17 (94%) gyrA mutants and 12/22 (55%) rrs mutants. Both assays showed comparable LODs for detecting rpoB and eis mutations; however, the SMB assay LODs were at least two logs better for detecting wild type and mutants in gyrA and rrs targets. The SMB assay was also moderately better at detecting heteroresistance. In summary, both assays appeared to be promising methods to detect drug resistance associated mutations in M. tuberculosis; however, the relative advantage of each assay varied under each test condition. PMID:25938476

  20. An isotopic approach to measuring nitrogen balance in caribou

    USGS Publications Warehouse

    Gustine, D.D.; Barboza, P.S.; Adams, L.G.; Farnell, R.G.; Parker, K.L.

    2011-01-01

    Nutritional restrictions in winter may reduce the availability of protein for reproduction and survival in northern ungulates. We refined a technique that uses recently voided excreta on snow to assess protein status in wild caribou (Rangifer tarandus) in late winter. Our study was the first application of this non-invasive, isotopic approach to assess protein status of wild caribou by determining dietary and endogenous contributions of nitrogen (N) to urinary urea. We used isotopic ratios of N (??15N) in urine and fecal samples to estimate the proportion of urea N derived from body N (p-UN) in pregnant, adult females of the Chisana Herd, a small population that ranged across the Alaska-Yukon border. We took advantage of a predator-exclosure project to examine N status of penned caribou in April 2006. Lichens were the primary forage (>40%) consumed by caribou in the pen and ?? 15N of fiber tracked the major forages in their diets. The ??15N of urinary urea for females in the pen was depleted relative (-1.3 ?? 1.0 parts per thousand [??], x?? ?? SD) to the ??15N of body N (2.7 ?? 0.7??). A similar proportion of animals in the exclosure lost core body mass (excluding estimates of fetal and uterine tissues; 55%) and body protein (estimated by isotope ratios; 54%). This non-invasive technique could be applied at various spatial and temporal scales to assess trends in protein status of free-ranging populations of northern ungulates. Intra- and inter-annual estimates of protein status could help managers monitor effects of foraging conditions on nutritional constraints in ungulates, increase the efficiency and efficacy of management actions, and help prepare stakeholders for potential changes in population trends. ?? 2010 The Wildlife Society.

  1. Description of C isotopes within RMF+BCS approach

    NASA Astrophysics Data System (ADS)

    Saxena, G.; Singh, D.; Kaushik, M.

    2013-06-01

    In the present investigations we have employed relativistic mean-field plus BCS (RMF + BCS) approach to carry out a systematic study for the ground state properties of even-even C Isotopes. One of the prime reason of this study has been to look into the role of low lying states in neutron rich reason near neutron drip line. It is found that irrespective of whether any resonant state exists or not, the occupancy of weakly bound neutron single particle states having low orbital angular momentum, (l = 0 or 1), with a well spread wave function due to the absence or very small strength of centrifugal barrier, helps to cause the occurrence of nuclei with widely extended neutron density. Such nuclei are found to have characteristically very small two-neutron separation energy and large neutron rms radius akin to that observed in weakly bound systems.

  2. Description of C isotopes within RMF+BCS approach

    SciTech Connect

    Saxena, G.; Singh, D.; Kaushik, M.

    2013-06-03

    In the present investigations we have employed relativistic mean-field plus BCS (RMF + BCS) approach to carry out a systematic study for the ground state properties of even-even C Isotopes. One of the prime reason of this study has been to look into the role of low lying states in neutron rich reason near neutron drip line. It is found that irrespective of whether any resonant state exists or not, the occupancy of weakly bound neutron single particle states having low orbital angular momentum, (l = 0 or 1), with a well spread wave function due to the absence or very small strength of centrifugal barrier, helps to cause the occurrence of nuclei with widely extended neutron density. Such nuclei are found to have characteristically very small two-neutron separation energy and large neutron rms radius akin to that observed in weakly bound systems.

  3. In Vivo Tumor Vasculature Targeted PET/NIRF Imaging with TRC105(Fab)-Conjugated, Dual-Labeled Mesoporous Silica Nanoparticles

    PubMed Central

    2015-01-01

    Multifunctional mesoporous silica nanoparticles (MSN) with well-integrated multimodality imaging properties have generated increasing research interest in the past decade. However, limited progress has been made in developing MSN-based multimodality imaging agents to image tumors. We describe the successful conjugation of, copper-64 (64Cu, t1/2 = 12.7 h), 800CW (a near-infrared fluorescence [NIRF] dye), and TRC105 (a human/murine chimeric IgG1 monoclonal antibody) to the surface of MSN via well-developed surface engineering procedures, resulting in a dual-labeled MSN for in vivo targeted positron emission tomography (PET) imaging/NIRF imaging of the tumor vasculature. Pharmacokinetics and tumor targeting efficacy/specificity in 4T1 murine breast tumor-bearing mice were thoroughly investigated through various in vitro, in vivo, and ex vivo experiments. Dual-labeled MSN is an attractive candidate for future cancer theranostics. PMID:24937108

  4. In vivo tumor vasculature targeted PET/NIRF imaging with TRC105(Fab)-conjugated, dual-labeled mesoporous silica nanoparticles.

    PubMed

    Chen, Feng; Nayak, Tapas R; Goel, Shreya; Valdovinos, Hector F; Hong, Hao; Theuer, Charles P; Barnhart, Todd E; Cai, Weibo

    2014-11-01

    Multifunctional mesoporous silica nanoparticles (MSN) with well-integrated multimodality imaging properties have generated increasing research interest in the past decade. However, limited progress has been made in developing MSN-based multimodality imaging agents to image tumors. We describe the successful conjugation of, copper-64 ((64)Cu, t1/2 = 12.7 h), 800CW (a near-infrared fluorescence [NIRF] dye), and TRC105 (a human/murine chimeric IgG1 monoclonal antibody) to the surface of MSN via well-developed surface engineering procedures, resulting in a dual-labeled MSN for in vivo targeted positron emission tomography (PET) imaging/NIRF imaging of the tumor vasculature. Pharmacokinetics and tumor targeting efficacy/specificity in 4T1 murine breast tumor-bearing mice were thoroughly investigated through various in vitro, in vivo, and ex vivo experiments. Dual-labeled MSN is an attractive candidate for future cancer theranostics. PMID:24937108

  5. Detection and Tracking of Dual-Labeled HIV Particles Using Wide-Field Live Cell Imaging to Follow Viral Core Integrity.

    PubMed

    Mamede, João I; Hope, Thomas J

    2016-01-01

    Live cell imaging is a valuable technique that allows the characterization of the dynamic processes of the HIV-1 life cycle. Here, we present a method of production and imaging of dual-labeled HIV viral particles that allows the visualization of two events. Varying release of the intravirion fluid phase marker reveals virion fusion and the loss of the integrity of HIV viral cores with the use of live wide-field fluorescent microscopy. PMID:26714704

  6. A dual-labeled Annexin A5 is not suited for SPECT imaging of brain cell death in experimental murine stroke

    PubMed Central

    Zille, Marietta; Harhausen, Denise; De Saint-Hubert, Marijke; Michel, Roger; Reutelingsperger, Chris P; Dirnagl, Ulrich; Wunder, Andreas

    2014-01-01

    Cell death is one of the pathophysiological hallmarks after stroke. Markers to image cell death pathways in vivo are highly desirable. We previously showed that fluorescently labeled Annexin A5 (AnxA5), which binds specifically to phosphatidylserine (PS) on dead/dying cells, can be used in experimental stroke for monitoring cell death with optical imaging. Here we investigated whether dual-labeled AnxA5 (technetium and fluorescence label) can be used for single-photon emission computed tomography (SPECT) of cell death in the same model. C57Bl6/N mice were subjected to 60-minute middle cerebral artery occlusion (MCAO) and underwent SPECT imaging at 24, 48, and 72 hours afterwards. They were injected intravenously with either PS-binding AnxA5 or the nonfunctional AnxA5 (negative control), labeled with 99mTc and Alexa Fluor 568, respectively. After SPECT imaging, brain sections were cut for autoradiography and fluorescence microscopy. Ethanol-induced cell death in the femur muscle was used as positive control. We detected dual-labeled AnxA5 in the model of ethanol-induced cell death in the femur muscle, but not after MCAO at any time point, either with SPECT or with ex vivo autoradiography or fluorescence microscopy. Dual-labeled AnxA5 appears to be unsuited for visualizing death of brain cells in this MCAO model. PMID:24984896

  7. Biomarker and molecular isotope approaches to deconvolve the terrestrial carbon isotope record: modern and Eocene calibrations

    NASA Astrophysics Data System (ADS)

    Diefendorf, A. F.; Freeman, K. H.; Wing, S.; Currano, E. D.

    2010-12-01

    Climate, biome, and plant community are important predictors of carbon isotope patterns recorded in leaves and leaf waxes. However, signatures recorded by terrestrial organic carbon and lipids that have mixed floral sources (e.g., n-alkanes) potentially reflect both plant community changes and climate. More taxonomically specific proxies for plants (i.e., di- and tri-terpenoids for conifers and angiosperms, respectively), can help to resolve the relative influences of changing community and climate, provided differences in biomarker production and lipid biosynthetic fractionation among plants can be better constrained. We present biomarker abundance and carbon isotope values for lipids from leaves, branches and bark of 44 tree species, representing 21 families including deciduous and evergreen conifers and angiosperms. n-alkane production differs greatly between conifer and angiosperm leaves. Both deciduous and evergreen angiosperms make significantly more n-alkanes than conifers, with n-alkanes not detected in over half of the conifers in our study. Terpenoid abundances scale strongly with leaf habit: evergreen species have significantly higher abundances. We combine these relative differences in lipid production with published estimates of fluxes for leaf litter from conifer and angiosperm trees to develop a new proxy approach for estimating paleo plant community inputs to ancient soils and sediments. To test our modern calibration results, we have evaluated n-alkanes and terpenoids from laterally extensive (~18 km) carbonaceous shales and mudstones in Eocene sediments (52.6 Ma) at Fifteenmile Creek in the Bighorn Basin (WY, USA). Our terpenoid-based proxy predicts on average a 40% conifer community, which is remarkably close in agreement with a fossil-based estimate of 36%. n-alkane carbon isotope fractionation (leaf-lipid) differs among plant types, with conifer n-alkanes about 2-3‰ 13C enriched relative to those in angiosperms. Since conifer leaves are

  8. Three dimensional dual labelled DNA fluorescent in situ hybridization analysis in fixed tissue sections

    PubMed Central

    Kernohan, Kristin D.; Bérubé, Nathalie G.

    2014-01-01

    Emerging studies demonstrate that three-dimensional organization of chromatin in the nucleus plays a vital role in regulating the genome. DNA fluorescent in situ hybridization (FISH) is a common molecular technique used to visualize the location of DNA sequences. The vast majority of DNA FISH studies are conducted on cultured cells due to the technical difficulties encountered using fixed tissue sections. However, the use of cultured cells poses important limitations that could yield misleading results, making in vivo analysis a far superior approach. Here we present a protocol for multiplexed three dimensional DNA FISH in mouse brain sections, which is also applicable to other tissues. Paraffin-embedded tissues could be used but the embedding and preparation of the samples is time-consuming and often associated with poor antigenicity. To overcome this problem we:•developed a FISH technique using fixed, frozen cryosections;•provide specific instructions for tissue processing for proper fixation and freezing, including equilibration in sucrose gradients to maintain proper cellular structure;•include optimized permeabilization and washing steps to achieve specific signal and to limit background fluorescence in tissue sections. PMID:26150931

  9. Isotope approach to assess hydrologic connections during Marcellus Shale drilling.

    PubMed

    Sharma, Shikha; Mulder, Michon L; Sack, Andrea; Schroeder, Karl; Hammack, Richard

    2014-01-01

    Water and gas samples were collected from (1) nine shallow groundwater aquifers overlying Marcellus Shale in north-central West Virginia before active shale gas drilling, (2) wells producing gas from Upper Devonian sands and Middle Devonian Marcellus Shale in southwestern Pennsylvania, (3) coal-mine water discharges in southwestern Pennsylvania, and (4) streams in southwestern Pennsylvania and north-central West Virginia. Our preliminary results demonstrate that the oxygen and hydrogen isotope composition of water, carbon isotope composition of dissolved inorganic carbon, and carbon and hydrogen isotope compositions of methane in Upper Devonian sands and Marcellus Shale are very different compared with shallow groundwater aquifers, coal-mine waters, and stream waters of the region. Therefore, spatiotemporal stable isotope monitoring of the different sources of water before, during, and after hydraulic fracturing can be used to identify migrations of fluids and gas from deep formations that are coincident with shale gas drilling. PMID:23772970

  10. Heavy element stable isotope ratios: analytical approaches and applications.

    PubMed

    Tanimizu, Masaharu; Sohrin, Yoshiki; Hirata, Takafumi

    2013-03-01

    Continuous developments in inorganic mass spectrometry techniques, including a combination of an inductively coupled plasma ion source and a magnetic sector-based mass spectrometer equipped with a multiple-collector array, have revolutionized the precision of isotope ratio measurements, and applications of inorganic mass spectrometry for biochemistry, geochemistry, and marine chemistry are beginning to appear on the horizon. Series of pioneering studies have revealed that natural stable isotope fractionations of many elements heavier than S (e.g., Fe, Cu, Zn, Sr, Ce, Nd, Mo, Cd, W, Tl, and U) are common on Earth, and it had been widely recognized that most physicochemical reactions or biochemical processes induce mass-dependent isotope fractionation. The variations in isotope ratios of the heavy elements can provide new insights into past and present biochemical and geochemical processes. To achieve this, the analytical community is actively solving problems such as spectral interference, mass discrimination drift, chemical separation and purification, and reduction of the contamination of analytes. This article describes data calibration and standardization protocols to allow interlaboratory comparisons or to maintain traceability of data, and basic principles of isotope fractionation in nature, together with high-selectivity and high-yield chemical separation and purification techniques for stable isotope studies. PMID:23397089

  11. Nitrogen isotopes in Tree-Rings - An approach combining soil biogeochemistry and isotopic long series with statistical modeling

    NASA Astrophysics Data System (ADS)

    Savard, Martine M.; Bégin, Christian; Paré, David; Marion, Joëlle; Laganière, Jérôme; Séguin, Armand; Stefani, Franck; Smirnoff, Anna

    2016-04-01

    Monitoring atmospheric emissions from industrial centers in North America generally started less than 25 years ago. To compensate for the lack of monitoring, previous investigations have interpreted tree-ring N changes using the known chronology of human activities, without facing the challenge of separating climatic effects from potential anthropogenic impacts. Here we document such an attempt conducted in the oil sands (OS) mining region of Northeastern Alberta, Canada. The reactive nitrogen (Nr)-emitting oil extraction operations began in 1967, but air quality measurements were only initiated in 1997. To investigate if the beginning and intensification of OS operations induced changes in the forest N-cycle, we sampled white spruce (Picea glauca (Moench) Voss) stands located at various distances from the main mining area, and receiving low, but different N deposition. Our approach combines soil biogeochemical and metagenomic characterization with long, well dated, tree-ring isotopic series. To objectively delineate the natural N isotopic behaviour in trees, we have characterized tree-ring N isotope (15N/14N) ratios between 1880 and 2009, used statistical analyses of the isotopic values and local climatic parameters of the pre-mining period to calibrate response functions and project the isotopic responses to climate during the extraction period. During that period, the measured series depart negatively from the projected natural trends. In addition, these long-term negative isotopic trends are better reproduced by multiple-regression models combining climatic parameters with the proxy for regional mining Nr emissions. These negative isotopic trends point towards changes in the forest soil biogeochemical N cycle. The biogeochemical data and ultimate soil mechanisms responsible for such changes will be discussed during the presentation.

  12. CD146-targeted immunoPET and NIRF Imaging of Hepatocellular Carcinoma with a Dual-Labeled Monoclonal Antibody

    PubMed Central

    Hernandez, Reinier; Sun, Haiyan; England, Christopher G.; Valdovinos, Hector F.; Ehlerding, Emily B.; Barnhart, Todd E.; Yang, Yunan; Cai, Weibo

    2016-01-01

    Overexpression of CD146 has been correlated with aggressiveness, recurrence rate, and poor overall survival in hepatocellular carcinoma (HCC) patients. In this study, we set out to develop a CD146-targeting probe for high-contrast noninvasive in vivo positron emission tomography (PET) and near-infrared fluorescence (NIRF) imaging of HCCs. YY146, an anti-CD146 monoclonal antibody, was employed as a targeting molecule to which we conjugated the zwitterionic near-infrared fluorescence (NIRF) dye ZW800-1 and the chelator deferoxamine (Df). This enabled labeling of Df-YY146-ZW800 with 89Zr and its subsequent detection using PET and NIRF imaging, all without compromising antibody binding properties. Two HCC cell lines expressing high (HepG2) and low (Huh7) levels of CD146 were employed to generate subcutaneous (s.c.) and orthotopic xenografts in athymic nude mice. Sequential PET and NIRF imaging performed after intravenous injection of 89Zr-Df-YY146-ZW800 into tumor-bearing mice unveiled prominent and persistent uptake of the tracer in HepG2 tumors that peaked at 31.65 ± 7.15 percentage of injected dose per gram (%ID/g; n=4) 72 h post-injection. Owing to such marked accumulation, tumor delineation was successful by both PET and NIRF, which facilitated the fluorescence image-guided resection of orthotopic HepG2 tumors, despite the relatively high liver background. CD146-negative Huh7 and CD146-blocked HepG2 tumors exhibited significantly lower 89Zr-Df-YY146-ZW800 accretion (6.1 ± 0.5 and 8.1 ± 1.0 %ID/g at 72 h p.i., respectively; n=4), demonstrating the CD146-specificity of the tracer in vivo. Ex vivo biodistribution and immunofluorescent staining corroborated the accuracy of the imaging data and correlated tracer uptake with in situ CD146 expression. Overall, 89Zr-Df-YY146-ZW800 showed excellent properties as a PET/NIRF imaging agent, including high in vivo affinity and specificity for CD146-expressing HCC. CD146-targeted molecular imaging using dual-labeled YY146

  13. CD146-targeted immunoPET and NIRF Imaging of Hepatocellular Carcinoma with a Dual-Labeled Monoclonal Antibody.

    PubMed

    Hernandez, Reinier; Sun, Haiyan; England, Christopher G; Valdovinos, Hector F; Ehlerding, Emily B; Barnhart, Todd E; Yang, Yunan; Cai, Weibo

    2016-01-01

    Overexpression of CD146 has been correlated with aggressiveness, recurrence rate, and poor overall survival in hepatocellular carcinoma (HCC) patients. In this study, we set out to develop a CD146-targeting probe for high-contrast noninvasive in vivo positron emission tomography (PET) and near-infrared fluorescence (NIRF) imaging of HCCs. YY146, an anti-CD146 monoclonal antibody, was employed as a targeting molecule to which we conjugated the zwitterionic near-infrared fluorescence (NIRF) dye ZW800-1 and the chelator deferoxamine (Df). This enabled labeling of Df-YY146-ZW800 with (89)Zr and its subsequent detection using PET and NIRF imaging, all without compromising antibody binding properties. Two HCC cell lines expressing high (HepG2) and low (Huh7) levels of CD146 were employed to generate subcutaneous (s.c.) and orthotopic xenografts in athymic nude mice. Sequential PET and NIRF imaging performed after intravenous injection of (89)Zr-Df-YY146-ZW800 into tumor-bearing mice unveiled prominent and persistent uptake of the tracer in HepG2 tumors that peaked at 31.65 ± 7.15 percentage of injected dose per gram (%ID/g; n=4) 72 h post-injection. Owing to such marked accumulation, tumor delineation was successful by both PET and NIRF, which facilitated the fluorescence image-guided resection of orthotopic HepG2 tumors, despite the relatively high liver background. CD146-negative Huh7 and CD146-blocked HepG2 tumors exhibited significantly lower (89)Zr-Df-YY146-ZW800 accretion (6.1 ± 0.5 and 8.1 ± 1.0 %ID/g at 72 h p.i., respectively; n=4), demonstrating the CD146-specificity of the tracer in vivo. Ex vivo biodistribution and immunofluorescent staining corroborated the accuracy of the imaging data and correlated tracer uptake with in situ CD146 expression. Overall, (89)Zr-Df-YY146-ZW800 showed excellent properties as a PET/NIRF imaging agent, including high in vivo affinity and specificity for CD146-expressing HCC. CD146-targeted molecular imaging using dual-labeled

  14. Tracing Cadmium in the Environment: an Evolving Stable Isotope Approach

    NASA Astrophysics Data System (ADS)

    Bullen, T. D.; Bouse, R. M.; Brown, C. L.; Croteau, M.; Luoma, S. N.; Topping, B. R.

    2005-05-01

    Cadmium (Cd) is a trace constituent in rocks and waters, and like many transition metals is an essential dietary nutrient at low levels but highly toxic in elevated doses. In many respects, cadmium behaves chemically like calcium (Ca) and thus substitutes for Ca in liquid-solid partitioning reactions and generally follows Ca through biogeochemical cycles and metabolic processes. Cd is comprised of 8 stable isotopes, and given the isotopic systematics of environmental Ca it is likely that variations in the stable isotope composition of Cd in natural materials will result from both inorganic and biologic processes. In order to assess the potential of Cd isotope variations to reveal information about sources, metabolic and biogeochemical pathways and fates of environmental Cd, we have initiated a broad study of the stable isotope composition of Cd in a variety of natural and anthropogenically-influenced systems. As an example, here we report the results of the first systematic study of the stable isotope composition of Cd in biologic materials. We focused on the isotopic variability of Cd in tissues of two species of clam collected from the San Francisco Bay estuary, Potamocorbula amurensis which resides in brackish water and Corbicula fluminea which resides in fresh and slightly brackish water. Both clam species concentrate Cd in their soft and hard tissues. During both low-flow conditions in August and high-flow conditions in April, δ116Cd of soft tissues of Potamocorbula was consistently negative and increased down-estuary with increasing salinity (δ116Cd is defined as the per mil difference of the 116Cd/110Cd ratio between a sample and our standard, igneous rock BIR-1). Samples collected in August were systematically displaced to higher δ116Cd than those collected in April. Soft tissues of Corbicula collected in both August and April from upstream, fully fresh-water sampling sites had identical δ116Cd, while soft tissues of Corbicula collected from our site at

  15. Quality analysis of in vivo near-infrared fluorescence and conventional gamma images acquired using a dual-labeled tumor-targeting probe.

    PubMed

    Houston, Jessica P; Ke, Shi; Wang, Wei; Li, Chun; Sevick-Muraca, Eva M

    2005-01-01

    The cyclic peptide, cyclopentapeptide cyclo(lys-Arg-Gly-Asp-phe) (c(KRGDf)), which is known to target alpha(v)beta3 integrin, is dual-labeled with a radiotracer, (111)indium, for gamma scintigraphy as well as with a near-infrared dye, IRDye800, for continuous-wave (cw) imaging of alpha(v)beta3 positive human M21 melanoma in xenografts. Twenty-four hours after administration of the dual-labeled peptide at a dose equivalent to 90 microCi of (111)In and 5 nmol of near-infrared (NIR) dye, whole-body gamma scintigraphy and cw imaging was conducted. Image acquisition time was 15 min for the gamma scintigraphy images and 800 ms for the optical images acquired using an NIR sensitive intensified charge-coupled device. The results show that while the target-to-background ratio (TBR) of nuclear and optical imaging were similar for surface regions of interest and consistent with the origin of gamma and NIR radiation from a common targeted peptide, the signal-to-noise ratio (SNR) was significantly higher for optical than nuclear imaging. Furthermore, an analysis of SNR versus contrast showed greater sensitivity of optical over nuclear imaging for the subcutaneous tumor targets. While tomographic reconstructions are necessary to probe TBR, SNR, and contrast for interior tissues, this work demonstrates for the first time the direct comparison of molecular optical and planar nuclear imaging for surface and subsurface cancers. PMID:16292970

  16. Uranium disequilibrium in groundwater: An isotope dilution approach in hydrologic investigations

    USGS Publications Warehouse

    Osmond, J.K.; Rydell, H.S.; Kaufman, M.I.

    1968-01-01

    The distribution and environmental disequilibrium patterns of naturally occurring uranium isotopes (U234 and U238) in waters of the Floridan aquifer suggest that variations in the ratios of isotopic activity and concentrations can be used quantitatively to evaluate mixing proportions of waters from differing sources. Uranium is probably unique in its potential for this approach, which seems to have general usefulness in hydrologic investigations.

  17. Uranium disequilibrium in groundwater: an isotope dilution approach in hydrologic investigations.

    PubMed

    Osmond, J K; Rydell, H S; Kaufman, M I

    1968-11-29

    The distribution and environmental disequilibrium patterns of naturally occurring uranium isotopes (U(234) and U(238)) in waters of the Floridan aquifer suggest that variations in the ratios of isotopic activity and concentrations can be used quantitatively to evaluate mixing proportions of waters from differing sources. Uranium is probably unique in its potential for this approach, which seems to have general usefulness in hydrologic investigations. PMID:4880720

  18. A gas chromatograph/mass spectrometry method for determining isotopic distributions in organic compounds used in the chemical approach to stable isotope separation

    SciTech Connect

    Martinez, A.M.; Spall, W.D.; Smith, B.F.

    1990-01-01

    A variety of gas chromatograph/mass spectrometry (GC/MS) methods have been developed to resolve benzene, benzophenone, anthracene, fluorenone, and their respective stable isotope analogs from other components by gas chromatography. The ratio of stable isotope-labeled material to natural isotopic abundance compounds is determined from the mass spectra averaged across the chromatographic peak. Both total ion and selective ion chromatographic approaches were used for relative data and comparison. 9 refs., 11 tabs.

  19. Quantification of in Situ Biodegradation Rate Constants Using a Novel Combined Isotope Approach

    NASA Astrophysics Data System (ADS)

    Blum, P.; Sültenfuß, J.; Martus, P.

    2014-12-01

    Numerous studies have shown the enormous potential of the compound-specific isotope analysis (CSIA) for studying the biodegradation of organic compounds such as monoaromatic hydrocarbons (BTEX), polyaromatic hydrocarbons (PAH), chlorinated solvents and other organic contaminants and environmental transformation mechanisms in groundwater. In addition, two-dimensional isotope analysis such as carbon and hydrogen have been successfully studied indicating the potential to also investigate site-specific reaction mechanisms. The main objective of the current study however is to quantify real effective in situ biodegradation rate constants in a coal-tar contaminated aquifer by combining compound-specific isotope analysis (CSIA) and tracer-based (3H-3He) ground-water dating (TGD). Hence, groundwater samples are used to determine groundwater residence times, and carbon and hydrogen stable isotopes are analyzed for selected BTEX and PAH. The results of the hydrogen stable isotopes surprisingly indicate no isotope fractionation and therefore no biodegradation. In contrast, for stable carbon isotopes of selected BTEX such as o-xylene and toluene, isotope shifts are detected indicating active biodegradation under sulfate-reducing conditions. These and previous results of stable carbon isotopes show that only for o-xylene a clear evidence for biodegradation is possible for the studied site. Nevertheless, in combining these results with the groundwater residence times, which range between 1 year for the shallow wells (20 m below surface) and 41 years for the deeper wells (40 m below surface), it is feasible to effectively determine in situ biodegradation rate constants for o-xylene. Conversely, the outcome also evidently demonstrate the major limitations of the novel combined isotope approach for a successful implementation of monitored natural attenuation (MNA) at such field sites.

  20. Where does streamwater come from in low relief forested watersheds? A dual isotope approach

    NASA Astrophysics Data System (ADS)

    Klaus, J.; McDonnell, J. J.; Jackson, C. R.; Du, E.; Griffiths, N. A.

    2014-03-01

    The time- and geographic sources of streamwater in low relief watersheds are poorly understood. This is partly due to the difficult combination of low runoff coefficients and often damped streamwater isotopic signals precluding traditional hydrograph separation and convolution integral approaches. Here we present a dual isotope approach involving 18O and 2H of water in a low angle forested watershed to determine streamwater source components and then build a conceptual model of streamflow generation. We focus on three headwater lowland sub-catchments draining the Savannah River Site in South Carolina, USA. Our results for a 3 year sampling period show that the slopes of the meteoric water lines/evaporation water lines (MWL/EWL) of the catchment water sources can be used to extract information on runoff source in ways not considered before. Our dual isotope approach was able to identify unique hillslope, riparian and deep groundwater, and streamflow compositions. The streams showed strong evaporative enrichment compared to the local meteoric water line (δ2H = 6.45 × δ18O + 6.26‰) with slopes of 2.52, 2.84, and 2.86. Based on the unique and unambiguous slopes of the EWLs of the different water cycle components and the isotopic time series of the individual components, we were able to show how the riparian zone controls baseflow in this system and how the riparian zone "resets" the stable isotope composition of the observed streams in our low angle, forested watersheds. Although this approach is limited in terms of quantifying mixing percentages between different end-members, our dual isotope approach enable extraction of hydrologically useful information in a region with little change in individual isotope time series.

  1. Where does streamwater come from in low-relief forested watersheds? A dual-isotope approach

    NASA Astrophysics Data System (ADS)

    Klaus, J.; McDonnell, J. J.; Jackson, C. R.; Du, E.; Griffiths, N. A.

    2015-01-01

    The time and geographic sources of streamwater in low-relief watersheds are poorly understood. This is partly due to the difficult combination of low runoff coefficients and often damped streamwater isotopic signals precluding traditional hydrograph separation and convolution integral approaches. Here we present a dual-isotope approach involving 18O and 2H of water in a low-angle forested watershed to determine streamwater source components and then build a conceptual model of streamflow generation. We focus on three headwater lowland sub-catchments draining the Savannah River Site in South Carolina, USA. Our results for a 3-year sampling period show that the slopes of the meteoric water lines/evaporation water lines (MWLs/EWLs) of the catchment water sources can be used to extract information on runoff sources in ways not considered before. Our dual-isotope approach was able to identify unique hillslope, riparian and deep groundwater, and streamflow compositions. The streams showed strong evaporative enrichment compared to the local meteoric water line (δ2H = 7.15 · δ18O +9.28‰) with slopes of 2.52, 2.84, and 2.86. Based on the unique and unambiguous slopes of the EWLs of the different water cycle components and the isotopic time series of the individual components, we were able to show how the riparian zone controls baseflow in this system and how the riparian zone "resets" the stable isotope composition of the observed streams in our low-angle, forested watersheds. Although this approach is limited in terms of quantifying mixing percentages between different end-members, our dual-isotope approach enabled the extraction of hydrologically useful information in a region with little change in individual isotope time series.

  2. Where does streamwater come from in low-relief forested watersheds? A dual-isotope approach

    SciTech Connect

    Klaus, J.; McDonnell, J. J.; Jackson, C. R.; Du, E.; Griffiths, N. A.

    2015-01-08

    The time and geographic sources of streamwater in low-relief watersheds are poorly understood. This is partly due to the difficult combination of low runoff coefficients and often damped streamwater isotopic signals precluding traditional hydrograph separation and convolution integral approaches. Here we present a dual-isotope approach involving 18O and 2H of water in a low-angle forested watershed to determine streamwater source components and then build a conceptual model of streamflow generation. We focus on three headwater lowland sub-catchments draining the Savannah River Site in South Carolina, USA. Our results for a 3-year sampling period show that the slopes of the meteoric water lines/evaporation water lines (MWLs/EWLs) of the catchment water sources can be used to extract information on runoff sources in ways not considered before. Our dual-isotope approach was able to identify unique hillslope, riparian and deep groundwater, and streamflow compositions. Thus, the streams showed strong evaporative enrichment compared to the local meteoric water line (δ2H = 7.15 · δ18O +9.28‰) with slopes of 2.52, 2.84, and 2.86. Based on the unique and unambiguous slopes of the EWLs of the different water cycle components and the isotopic time series of the individual components, we were able to show how the riparian zone controls baseflow in this system and how the riparian zone "resets" the stable isotope composition of the observed streams in our low-angle, forested watersheds. Although this approach is limited in terms of quantifying mixing percentages between different end-members, our dual-isotope approach enabled the extraction of hydrologically useful information in a region with little change in individual isotope time series.

  3. Where does streamwater come from in low-relief forested watersheds? A dual-isotope approach

    DOE PAGESBeta

    Klaus, J.; McDonnell, J. J.; Jackson, C. R.; Du, E.; Griffiths, N. A.

    2015-01-08

    The time and geographic sources of streamwater in low-relief watersheds are poorly understood. This is partly due to the difficult combination of low runoff coefficients and often damped streamwater isotopic signals precluding traditional hydrograph separation and convolution integral approaches. Here we present a dual-isotope approach involving 18O and 2H of water in a low-angle forested watershed to determine streamwater source components and then build a conceptual model of streamflow generation. We focus on three headwater lowland sub-catchments draining the Savannah River Site in South Carolina, USA. Our results for a 3-year sampling period show that the slopes of the meteoricmore » water lines/evaporation water lines (MWLs/EWLs) of the catchment water sources can be used to extract information on runoff sources in ways not considered before. Our dual-isotope approach was able to identify unique hillslope, riparian and deep groundwater, and streamflow compositions. Thus, the streams showed strong evaporative enrichment compared to the local meteoric water line (δ2H = 7.15 · δ18O +9.28‰) with slopes of 2.52, 2.84, and 2.86. Based on the unique and unambiguous slopes of the EWLs of the different water cycle components and the isotopic time series of the individual components, we were able to show how the riparian zone controls baseflow in this system and how the riparian zone "resets" the stable isotope composition of the observed streams in our low-angle, forested watersheds. Although this approach is limited in terms of quantifying mixing percentages between different end-members, our dual-isotope approach enabled the extraction of hydrologically useful information in a region with little change in individual isotope time series.« less

  4. Coupled sulfur isotopic and chemical mass transfer modeling: Approach and application to dynamic hydrothermal processes

    SciTech Connect

    Janecky, D.R.

    1988-09-21

    A computational modeling code (EQPSreverse arrowS) has been developed to examine sulfur isotopic distribution pathways coupled with calculations of chemical mass transfer pathways. A post processor approach to EQ6 calculations was chosen so that a variety of isotopic pathways could be examined for each reaction pathway. Two types of major bounding conditions were implemented: (1) equilibrium isotopic exchange between sulfate and sulfide species or exchange only accompanying chemical reduction and oxidation events, and (2) existence or lack of isotopic exchange between solution species and precipitated minerals, parallel to the open and closed chemical system formulations of chemical mass transfer modeling codes. All of the chemical data necessary to explicitly calculate isotopic distribution pathways is generated by most mass transfer modeling codes and can be input to the EQPS code. Routines are built in to directly handle EQ6 tabular files. Chemical reaction models of seafloor hydrothermal vent processes and accompanying sulfur isotopic distribution pathways illustrate the capabilities of coupling EQPSreverse arrowS with EQ6 calculations, including the extent of differences that can exist due to the isotopic bounding condition assumptions described above. 11 refs., 2 figs.

  5. A new approach to simulating stream isotope dynamics using Markov switching autoregressive models

    NASA Astrophysics Data System (ADS)

    Birkel, Christian; Paroli, Roberta; Spezia, Luigi; Dunn, Sarah M.; Tetzlaff, Doerthe; Soulsby, Chris

    2012-09-01

    In this study we applied Markov switching autoregressive models (MSARMs) as a proof-of-concept to analyze the temporal dynamics and statistical characteristics of the time series of two conservative water isotopes, deuterium (δ2H) and oxygen-18 (δ18O), in daily stream water samples over two years in a small catchment in eastern Scotland. MSARMs enabled us to explicitly account for the identified non-linear, non-Normal and non-stationary isotope dynamics of both time series. The hidden states of the Markov chain could also be associated with meteorological and hydrological drivers identifying the short (event) and longer-term (inter-event) transport mechanisms for both isotopes. Inference was based on the Bayesian approach performed through Markov Chain Monte Carlo algorithms, which also allowed us to deal with a high rate of missing values (17%). Although it is usually assumed that both isotopes are conservative and exhibit similar dynamics, δ18O showed somewhat different time series characteristics. Both isotopes were best modelled with two hidden states, but δ18O demanded autoregressions of the first order, whereas δ2H of the second. Moreover, both the dynamics of observations and the hidden states of the two isotopes were explained by two different sets of covariates. Consequently use of the two tracers for transit time modelling and hydrograph separation may result in different interpretations on the functioning of a catchment system.

  6. A dual-isotope approach to allow conclusive partitioning between three sources

    PubMed Central

    Whitman, Thea; Lehmann, Johannes

    2015-01-01

    Stable isotopes have proved to be a transformative tool; their application to distinguish between two sources in a mixture has been a cornerstone of biogeochemical research. However, quantitatively partitioning systems using two stable isotopes (for example, 13C and 12C) has been largely limited to only two sources, and systems of interest often have more than two components, with interactive effects. Here we introduce a dual-isotope approach to allow conclusive partitioning between three sources, using only two stable isotopes. We demonstrate this approach by partitioning soil CO2 emissions derived from microbial mineralization of soil organic carbon (SOC), added pyrogenic organic matter (PyOM) and root respiration. We find that SOC mineralization in the presence of roots is 23% higher (P<0.05) when PyOM is also present. Being able to discern three sources with two isotopes will be of great value not only in biogeochemical research, but may also expand hitherto untapped methodologies in diverse fields. PMID:26530521

  7. New approach to global barium cycle understanding: barium isotopic composition of marine carbonates and seawater.

    NASA Astrophysics Data System (ADS)

    Pretet, Chloé; Nägler, Thomas F.; Reynaud, Stéphanie; de Lange, Gert J.; Turpin, Mélanie; Immenhauser, Adrian; Böttcher, Michael E.; Samankassou, Elias

    2013-04-01

    In this communication we present the Ba isotope fractionation (delta137/134Ba) study on marine carbonates and seawater, initiated to gain a first order view of the marine Ba isotope cycle. A special focus is the question whether the nutrient type distribution of Ba in the water column, as well as different Ba sources, are reflected in Ba isotope ratios of carbonate archives. The approach ultimately aims to provide an improved Ba based paleonutrient proxy. The data set is composed of carbonates (micrites and limestone standard), coral skeleton and seawater (IAPSO standard and Mediterranean seawater). Part of the corals were cultured in monitored environments (CSM, Monaco) others originate from natural environments (shallow and warm water corals from the Bahamas/Florida and cold water corals from the Norwegian shelf). The analytical procedure includes the application of a 130Ba/135Ba double spike, a cation exchange column followed by isotope measurements on a Nu Instruments Multicollector ICP-MS. The Ba fractionation of the samples is compared to a Ba nitrate standard solution and a standard natural limestone BSC-CRM 393 (0.05 ± 0.04 ‰, 2SEM). No isotopic fractionation has been observed in the limestone standard and micrites (N=8) (-0.01 ± 0.04 ‰, 2SEM) compared to the Ba nitrate standard. On the contrary, coral skeletons show a significant positive fractionation (mean = 0.4 ± 0.05 ‰, 2 SEM). No significant difference was found between different cultured coral species. Thus no species-specific fractionation is identified within the same environmental conditions. Diagenetic influence on Ba isotopic composition was further tested on 5 natural samples with varying calcite to aragonite ratios (0 to 0.3). No significant effect was observed. Moreover, the Ba isotope composition seems independant from the Ba concentration in the studied coral skeleton, within our measurement resolution. Seawater isotopic composition (-0.05 ± 0.07 ‰, 2SD) is lighter than coral

  8. A new approach to quantifying internal diffusion resistances and CO2 isotope exchange in leaves

    NASA Astrophysics Data System (ADS)

    West, Jason; Ogée, Jérôme; Burlett, Régis; Gimeno, Teresa; Genty, Bernard; Jones, Samuel; Wohl, Steven; Bosc, Alexandre; Wingate, Lisa

    2016-04-01

    The oxygen isotopic composition (δ18O) of atmospheric CO2 can constrain the global CO2 budget at a range of scales, offering the potential to partition net CO2 exchanges into their component gross fluxes and provide insights to linkages between C and water cycles. However, there are significant limitations to utilizing the δ18O of CO2 to constrain C budgets because of uncertainties associated with the isotopic exchange of CO2 with terrestrial water pools. Leaf water in particular represents a critical pool with ongoing debates about its enrichment in heavy isotopes during transpiration and the hydration of CO2 and its oxygen isotope exchange with this pool. Isotopic heterogeneity of the leaf water, the spatial distribution and activity of carbonic anhydrase (CA) within leaves, and resistance to diffusion of CO2 from the substomatal cavity to chloroplasts are all key components with important uncertainties. Better constraints on these would significantly improve our ability to understand and model the global C budget as well as yield insights to fundamental aspects of leaf physiology. We report results using a new measurement system that permits the simultaneous measurement of the 13C and 18O composition of CO2 and the 18O isotopic composition of leaf transpiration. As this new approach permits rapid alteration of the isotopic composition of gases interacting with the leaf, key model parameters can be derived directly and simultaneously. Hence, our approach dos not rely on separate measurements shifted in time from the gas exchange measurements or that may not quantify the relevant scale of heterogeneity (e.g., CA enzyme assays or bulk leaf water extraction and analysis). In particular, this new method explicitly distinguishes the leaf mesophyll resistance to CO2 transport relevant for photosynthesis from the resistance required for interpreting the δ18O of CO2 and allows us to derive other relevant parameters directly. This new measurement system and modeling

  9. A Triple-Isotope Approach to Predict the Breeding Origins of European Bats

    PubMed Central

    Popa-Lisseanu, Ana G.; Sörgel, Karin; Luckner, Anja; Wassenaar, Leonard I.; Ibáñez, Carlos; Kramer-Schadt, Stephanie; Ciechanowski, Mateusz; Görföl, Tamás; Niermann, Ivo; Beuneux, Grégory; Mysłajek, Robert W.; Juste, Javier; Fonderflick, Jocelyn; Kelm, Detlev H.; Voigt, Christian C.

    2012-01-01

    Despite a commitment by the European Union to protect its migratory bat populations, conservation efforts are hindered by a poor understanding of bat migratory strategies and connectivity between breeding and wintering grounds. Traditional methods like mark-recapture are ineffective to study broad-scale bat migratory patterns. Stable hydrogen isotopes (δD) have been proven useful in establishing spatial migratory connectivity of animal populations. Before applying this tool, the method was calibrated using bat samples of known origin. Here we established the potential of δD as a robust geographical tracer of breeding origins of European bats by measuring δD in hair of five sedentary bat species from 45 locations throughout Europe. The δD of bat hair strongly correlated with well-established spatial isotopic patterns in mean annual precipitation in Europe, and therefore was highly correlated with latitude. We calculated a linear mixed-effects model, with species as random effect, linking δD of bat hair to precipitation δD of the areas of hair growth. This model can be used to predict breeding origins of European migrating bats. We used δ13C and δ15N to discriminate among potential origins of bats, and found that these isotopes can be used as variables to further refine origin predictions. A triple-isotope approach could thereby pinpoint populations or subpopulations that have distinct origins. Our results further corroborated stable isotope analysis as a powerful method to delineate animal migrations in Europe. PMID:22291947

  10. Fingerprints of environmental stressors in three selected Slovenian gravel-bed rivers: geochemical and isotopic approach

    NASA Astrophysics Data System (ADS)

    Kanduč, Tjaša; Kocman, David; Debeljak, Barbara; Mori, Nataša

    2016-04-01

    Rivers are severely impacted by a range of simultaneous processes including water pollution, flow and channel alteration, over-fishing, invasive species and climate change. Systematic studies of river water geochemistry provide important information on chemical weathering of bedrock/soil and natural anthropogenic processes that may control the dissolved chemical loads, while the isotopic studies of biological components of river systems (macrophytes, periphyton, heterotrophic biofilm, invertebrates, fish) contribute to the understanding how the system response to human impacts by means of functional response. In this contribution, insights in the fingerprints of various environmental stressors in three gravel-bed rivers (River Kamni\\vska Bistrica, River Idrijca and River Sava) in Slovenia, using geochemical and stable isotope approach are discussed. Gravel bed of all three rivers investigated is composed of carbonates and clastic rocks. The Sava and Kamni\\vska Bistrica Rivers have alpine high mountain snow-rain regime. The Idrijca River is a boundary river between the Adriatic and Black Sea catchments and has rain-snow discharge regime with torrential character. Geochemical methods (ICP-OES, IC, total alkalinity after Gran) and isotope mass - spectrometric methods (isotopic composition of dissolved inorganic carbon, particulate organic carbon and isotopic composition of carbon in carbonates) were used to evaluate biogeochemical processes in rivers. Isotopic composition of carbon and nitrogen of the moss Fontinalis antipyretica (the whole vegetative shoot) and isotopic composition of carbon of heterotrophic biofilm was also analyzed in order to better understand the fluxes and fractionation of carbon and nitrogen across trophic levels. Geochemical composition of all investigated rivers is HCO3‑-Ca2+-Mg2+ with different Mg2+/Ca2+ ratios as follows: around 0.33 for Kamni\\vska Bistrica and River Sava in Slovenia and above 0.75 for River Idrijca. In the Kamni

  11. Iron isotope fractionation between aqueous Fe(II) and goethite revisited: New insights based on a multi-direction approach to equilibrium and isotopic exchange rate modification

    NASA Astrophysics Data System (ADS)

    Frierdich, Andrew J.; Beard, Brian L.; Reddy, Thiruchelvi R.; Scherer, Michelle M.; Johnson, Clark M.

    2014-08-01

    The Fe isotope compositions of naturally occurring Fe oxide minerals provide insights into biogeochemical processes that occur in modern and ancient environments. Key to understanding isotopic variations in such minerals is knowledge of the equilibrium Fe isotope fractionation factors between common minerals and aqueous Fe species. Because experimental measurements of isotopic fractionation may reflect a combination of kinetic and equilibrium fractionations during rapid dissolution and precipitation, even in experiments that employ the three-isotope method, assessment of the attainment of equilibrium is often difficult. Here, we re-examine Fe isotope exchange, via a 57Fe tracer, and natural mass-dependent fractionation, through changes in initial 56Fe/54Fe ratios, between aqueous Fe(II) (Fe(II)aq) and goethite. This approach uses the three-isotope method, but is distinct in its evaluation of kinetic isotope fractionation and the attainment of equilibrium by: (i) employing a multi-direction approach to equilibrium at 22 °C via reaction of three Fe(II)aq solutions that had different initial 56Fe/54Fe ratios, (ii) conducting isotopic exchange experiments at elevated temperature (50 °C), and (iii) modifying the rate of isotopic exchange through a combination of trace-element substitutions and particle coarsening to evaluate corresponding temporal changes in fractionation trajectories that may reflect changing instantaneous fractionation factors. We find that rapid isotopic exchange produces kinetic isotope effects between Fe(II)aq and goethite, which shifts the 56Fe/54Fe ratios of Fe(II)aq early in reactions toward that of goethite, indicating that the instantaneous Fe(II)aq-goethite fractionation factor under kinetic conditions is small. Importantly, however, this kinetic fractionation is “erased” with continued reaction, and this is evident by the congruence for multiple-exchange trajectories of distinct initial Fe(II)aq solutions toward the same final value

  12. Investigation of tubular handling of bicarbonate in man. A new approach utilizing stable carbon isotope fractionation.

    PubMed Central

    Burbea, Z H; Luz, B; Lazar, B; Winaver, J; Better, O S

    1983-01-01

    Two alternative mechanisms have been proposed for tubular reabsorption of bicarbonate: (a) H+ secretion and CO2 reabsorption and (b) direct reabsorption of HCO-3. In an attempt to differentiate between the two mechanisms, the present study utilized the natural abundance of stable carbon isotopes (13C, 12C) in the urinary total CO2. This novel methodology used mass spectrometric analysis of 13C/12C ratios in urinary total CO2 under normal conditions and during acetazolamide treatment. Blood and respiratory CO2 were analyzed to yield reference values. The results demonstrate that alkaline urine is preferentially enriched with 13C relative to the blood. It is suggested that this fractionation results from reaction out of isotopic equilibrium in which HCO-3 converts to CO2 during the reabsorption process in the distal nephron. The presence of carbonic anhydrase in the proximal nephron results in rapid isotopic exchange between CO2 and HCO-3 and keeps them in isotopic equilibrium. The ratio of urinary 13C/12C increases strikingly after acetazolamide administration and consequent inhibition of carbonic anhydrase in the proximal tubule. Although it is possible that in the latter case high HCO-3 generates the CO2 (ampholyte effect), the isotope fractionation indicates that CO2 rather than HCO-3 is reabsorbed. In contrast, at low urinary pH and total CO2 values, the carbon isotope composition approaches that of blood CO2. This indicates rapid CO2 exchange between urine and blood, through luminal membrane highly permeable to CO2. These results could be anticipated by a mathematical model constructed to plot 13C concentration of urinary total CO2. It is concluded that the mechanism of HCO-3 reclamation in man (and, by inference, in other mammals as well) works by conversion of HCO-3 to CO2 and reabsorption of CO2. PMID:6417168

  13. Does Miscanthus cultivation on organic soils compensate for carbon loss from peat oxidation? A dual label study

    NASA Astrophysics Data System (ADS)

    Bader, Cédric; Leifeld, Jens; Müller, Moritz; Schulin, Rainer

    2016-04-01

    Agricultural use of organic soils requires drainage and thereby changes conditions in these soils from anoxic to oxic. As a consequence, organic carbon that had been accumulated over millennia is rapidly mineralized, so that these soils are converted from a CO2 sink to a source. The peat mineralization rate depends mainly on drainage depth, but also on crop type. Various studies show that Miscanthus, a C4 bioenergy plant, shows potential for carbon sequestration in mineral soils because of its high productivity, its dense root system, absence of tillage and high preharvest litterfall. If Miscanthus cropping would have a similar effect in organic soils, peat consumption and thus CO2 emissions might be reduced. For our study we compared two adjacent fields, on which organic soil is cultivated with Miscanthus (since 20 years) and perennial grass (since 6 years). Both sites are located in the Bernese Seeland, the largest former peatland area of Switzerland. To determine wether Miscanthus-derived carbon accumulated in the organic soil, we compared the stable carbon isotopic signatures of the experimental soil with those of an organic soil without any C4-plant cultivation history. To analyze the effect of C4-C accumulation on peat degradability we compared the CO2 emissions by incubating 90 soil samples of the two fields for more than one year. Additionally, we analysed the isotopic CO2 composition (13C, 14C) during the first 25 days of incubation after trapping the emitted CO2 in NaOH and precipitating it as BaCO3. The ∂13C values of the soil imply, that the highest share of C4-C of around 30% is situated at a depth of 10-20 cm. Corn that used to be cultivated on the grassland field before 2009 still accounts for 8% of SOC. O/C and H/C ratios of the peat samples indicate a stronger microbial imprint of organic matter under Miscanthus cultivation. The amount of CO2 emitted was not affected by the cultivation type. On average 57% of the CO2 was C4 derived in the

  14. Vibrationally averaged post Born-Oppenheimer isotopic dipole moment calculations approaching spectroscopic accuracy

    NASA Astrophysics Data System (ADS)

    Arapiraca, A. F. C.; Jonsson, Dan; Mohallem, J. R.

    2011-12-01

    We report an upgrade of the Dalton code to include post Born-Oppenheimer nuclear mass corrections in the calculations of (ro-)vibrational averages of molecular properties. These corrections are necessary to achieve an accuracy of 10-4 debye in the calculations of isotopic dipole moments. Calculations on the self-consistent field level present this accuracy, while numerical instabilities compromise correlated calculations. Applications to HD, ethane, and ethylene isotopologues are implemented, all of them approaching the experimental values.

  15. Vibrationally averaged post Born-Oppenheimer isotopic dipole moment calculations approaching spectroscopic accuracy.

    PubMed

    Arapiraca, A F C; Jonsson, Dan; Mohallem, J R

    2011-12-28

    We report an upgrade of the Dalton code to include post Born-Oppenheimer nuclear mass corrections in the calculations of (ro-)vibrational averages of molecular properties. These corrections are necessary to achieve an accuracy of 10(-4) debye in the calculations of isotopic dipole moments. Calculations on the self-consistent field level present this accuracy, while numerical instabilities compromise correlated calculations. Applications to HD, ethane, and ethylene isotopologues are implemented, all of them approaching the experimental values. PMID:22225162

  16. Progress in Quantifying Rates and Product Ratios of Microbial Denitrification Using Stable Isotope Approaches

    NASA Astrophysics Data System (ADS)

    Well, R.; Braker, G.; Buchen, C.; Giesemann, A.; Lewicka-Szczebak, D.; Rohe, L.; Flessa, H.

    2014-12-01

    Although it is known since long that microbial denitrification plays a central role in N cycling in soils due to loss of nutrient N, emissions of N2O and lowering of N leaching, few data at the field scale are available due to the difficulty in measurement. In recent years, stable isotope signatures of N2O such as d18O, average d15N (d15Nbulk) and 15N site preference (SP = difference in d15N between the central and peripheral N positions of the asymmetric N2O molecule) have been used to constrain the atmospheric N2O budget and to characterize N2O turnover processes including N2O production and reduction by microbial denitrification. However, the use of this approach to study N2O dynamics in soils requires knowledge of isotope fractionation factors for the various partial processes involved, e.g. N2O production by nitrification or fungal/bacterial denitrification, and N2O reduction by bacterial denitrification. Here we present recent progress on the principles of isotope fractionation modeling to estimate N2O reduction and on the role of microbial groups and their specific impact on isotope values. Moreover, we report and discuss approaches to determine isotope values of produced N2O prior to its reduction as well as enrichment factors of N2O reduction. Finally, a variety of results from lab and field studies will be shown were N2O reduction estimates by isotope fractionation modeling are validated by independent measurements using 15N tracing or He/O2 incubations. Methodical improvements to increase sensitivity of the 15N tracing approach will be briefly addressed. We conclude that up to now SP of soil-emitted N2O proved to be suitable to constrain the product ratio of denitrification if N2O fluxes are dominated by bacterial denitrification. Although this approach is not yet precise enough for robust quantification of N2 fluxes, improved precision can be obtained in future, if further progress in understanding the control of fractionation factors of production and

  17. Study of Density and Structure of Oxygen Isotopes with the Cluster-Orbital Shell Model Approach

    NASA Astrophysics Data System (ADS)

    Masui, Hiroshi; Kato, Kiyoshi; Ikeda, Kiyomi

    2009-10-01

    We study structure of oxygen isotopes through the analysis of the density and the s-wave contribution. From experiments, the r.m.s.radius of oxygen isotopes has an abrupt increase at ^23O from the empirical A^1/3-low. However, as we have shown with the calculation by using our m-scheme cluster-orbital shell model (COSM) approach, such the abrupt increase can hardly be reproduced only by considering the valence nucleon degree of freedom. In our COSM approach, we construct the core-N Hamiltonian using a semi-microscopic approach by taking into account the Pauli principle for the nucleons in the core. As the nucleon-nucleon potential, we use Volkov No.2 potential. The parameters of the potential are adjusted so as to reproduce the ^16O+2n threshold. Using the potential model described above, however, we obtain the over bound nature as the number of valence nucleon increase. Hence, we perform calculations using slightly weaker potential strength for the valence neutrons so as to reproduce the drip-line at ^24O. In this study, we discuss the density distributions of the isotopes and the contributions of partial waves especially the s-wave.

  18. A novel multiplex RT-qPCR method based on dual-labelled probes suitable for typing all known genotypes of viral haemorrhagic septicaemia virus.

    PubMed

    Vázquez, D; López-Vázquez, C; Skall, H F; Mikkelsen, S S; Olesen, N J; Dopazo, C P

    2016-04-01

    Viral haemorrhagic septicaemia (VHS) is a notifiable fish disease, whose causative agent is a rhabdovirus isolated from a wide range of fish species, not only in fresh but also in marine and brackish waters. Phylogenetic studies have identified four major genotypes, with a strong geographical relationship. In this study, we have designed and validated a new procedure - named binary multiplex RT-qPCR (bmRT-qPCR) - for simultaneous detection and typing of all four genotypes of VHSV by real-time RT-PCR based on dual-labelled probes and composed by two multiplex systems designed for European and American/Asiatic isolates, respectively, using a combination of three different fluorophores. The specificity of the procedure was assessed by including a panel of 81 VHSV isolates covering all known genotypes and subtypes of the virus, and tissue material from experimentally infected rainbow trout, resulting in a correct detection and typing of all strains. The analytical sensitivity was evaluated in a comparative assay with titration in cell culture, observing that both methods provided similar limits of detection. The proposed method can be a powerful tool for epidemiological analysis of VHSV by genotyping unknown samples within a few hours. PMID:25952496

  19. Simultaneous Detection of Forbidden Chemical Residues in Milk Using Dual-Label Time-Resolved Reverse Competitive Chemiluminescent Immunoassay Based on Amine Group Functionalized Surface

    PubMed Central

    Jiang, Haiyang; Wen, Kai; Shen, Jianzhong; Cao, Xingyuan

    2014-01-01

    In this study, a sensitive dual-label time-resolved reverse competitive chemiluminescent immunoassay was developed for simultaneous detection of chloramphenicol (CAP) and clenbuterol (CLE) in milk. The strategy was performed based on the distinction of the kinetic characteristics of horseradish peroxidase (HRP) and alkaline phosphatase (ALP) in chemiluminesecence (CL) systems and different orders of magnitude in HRP CL value for CAP and ALP CL value for CLE in the chemiluminescent immunoassay. Capture antibodies were covalently bound to the amine group functionalized chemiluminescent microtiter plate (MTP) for efficient binding of detection antibodies for the enzymes labeled CAP (HRP-CAP) and CLE (ALP-CLE). The CL signals were recorded at different time points by the automatic luminometers with significant distinction in the dynamic curves. When we considered the ALP CL value (about 105) of CLE as background for HRP CL signal value (about 107) of CAP, there was no interaction from ALP CL background of CLE and the differentiation of CAP and CLE can be easily achieved. The 50% inhibition concentration (IC50) values of CAP and CLE in milk samples were 0.00501 µg L−1 and 0.0128 µg L−1, with the ranges from 0.0003 µg L−1 to 0.0912 µg L−1 and from 0.00385 µg L−1 to 0.125 µg L−1, respectively. The developed method is more sensitive and of less duration than the commercial ELISA kits, suitable for simultaneous screening of CAP and CLE. PMID:25313517

  20. Nitrogen sources and cycling in the San Francisco Bay estuary: A nitrate dual isotopic composition approach

    USGS Publications Warehouse

    Wankel, Scott D.; Kendall, C.; Francis, C.A.; Paytan, A.

    2006-01-01

    We used the dual isotopic composition of nitrate (??15N and ??18O) within the estuarine system of San Francisco (SF) Bay, California, to explore the utility of this approach for tracing sources and cycling of nitrate (NO3-). Surface water samples from 49 sites within the estuary were sampled during July-August 2004. Spatial variability in the isotopic composition suggests that there are multiple sources of nitrate to the bay ecosystem including seawater, several rivers and creeks, and sewage effluent. The spatial distribution of nitrate from these sources is heavily modulated by the hydrodynamics of the estuary. Mixing along the estuarine salinity gradient is the main control on the spatial variations in isotopic composition of nitrate within the northern arm of SF Bay. However, the nitrate isotopic composition in the southern arm of SF Bay exhibited a combination of source mixing and phytoplankton drawdown due mostly to the long residence time during the summer study period. Very low ?? 18ONO3 values (as low as -5.0???) at the Sacramento-San Joaquin River delta region give rise to a wide range of ??18ONO3 values in the SF Bay system. The range in ??18ONO3 values is more than twice that of (??15NNO3, suggesting that ??18O NO3 is an even more sensitive tool for tracing nitrate sources and cycling than ??15NNO3. ?? 2006, by the American Society of Limnology and Oceanography, Inc.

  1. An analytical approach to Sr isotope ratio determination in Lambrusco wines for geographical traceability purposes.

    PubMed

    Durante, Caterina; Baschieri, Carlo; Bertacchini, Lucia; Bertelli, Davide; Cocchi, Marina; Marchetti, Andrea; Manzini, Daniela; Papotti, Giulia; Sighinolfi, Simona

    2015-04-15

    Geographical origin and authenticity of food are topics of interest for both consumers and producers. Among the different indicators used for traceability studies, (87)Sr/(86)Sr isotopic ratio has provided excellent results. In this study, two analytical approaches for wine sample pre-treatment, microwave and low temperature mineralisation, were investigated to develop accurate and precise analytical method for (87)Sr/(86)Sr determination. The two procedures led to comparable results (paired t-test, with tisotopic values were compared with isotopic data coming from (i) soils of their territory of origin and (ii) wines obtained by same grape varieties cultivated in different districts. The obtained results have shown no significant variability among the different vintages of wines and a perfect agreement between the isotopic range of the soils and wines has been observed. Nevertheless, the investigated indicator was not enough powerful to discriminate between similar products. To this regard, it is worth to note that more soil samples as well as wines coming from different districts will be considered to obtain more trustworthy results. PMID:25466059

  2. Progress in quantifying rates and product ratios of microbial denitrification using stable isotope approaches

    NASA Astrophysics Data System (ADS)

    Well, Reinhard; Buchen, Caroline; Giesemann, Anette; Lewicka-Szczebak, Dominika; Rohe, Lena; Flessa, Heinz

    2015-04-01

    Although it is known since long that microbial denitrification plays a central role in N cycling in soils due to loss of nutrient N, emissions of N2O and lowering of N leaching, few data at the field scale are available due to the difficulty in measurement. In recent years, stable isotope signatures of N2O such as δ18O, average δ15N (δ15Nbulk) and 15N site preference (SP = difference in δ15N between the central and peripheral N positions of the asymmetric N2O molecule) have been used to constrain the atmospheric N2O budget and to characterize N2O turnover processes including N2O production and reduction by microbial denitrification. However, the use of this approach to study N2O dynamics in soils requires knowledge of isotope fractionation factors for the various partial processes involved, e.g. N2O production by nitrification or fungal/bacterial denitrification, and N2O reduction by bacterial denitrification. Here we present recent progress on the principles of isotope fractionation modeling to estimate N2O reduction and on the role of microbial groups and their specific impact on isotope values. Moreover, we report and discuss approaches to determine isotope values of produced N2O prior to its reduction as well as enrichment factors of N2O reduction. Finally, a variety of results from lab and field studies will be shown were N2O reduction estimates by isotope fractionation modeling are validated by independent measurements using 15N tracing or He/O2 incubations. Methodical improvements to increase sensitivity of the 15N tracing approach will be briefly addressed. We conclude that up to now SP of soil-emitted N2O proved to be suitable to constrain the product ratio of denitrification if N2O fluxes are dominated by bacterial denitrification. Although this approach is not yet precise enough for robust quantification of N2 fluxes, improved precision can be obtained in future, if further progress in understanding the control of fractionation factors of production

  3. A simplified methodology to approach the complexity of foraminiferal calcite oxygen-isotope data - model comparison

    NASA Astrophysics Data System (ADS)

    Roche, Didier; Waelbroeck, Claire

    2016-04-01

    Since the pioneering work of Epstein (Epstein et al., 1953), numerous calcite isotopic records from the ocean have been used to attempt reconstructing paleoclimatic information. Additional to the well known complexity brought by the fact that foraminiferal calcite records both temperature and isotopic composition of the surrounding oceanic waters, an additional effect for surface - dwelling foraminifers is the fact that two different species do not have the same habitat and may thus record different signals. This is obvious when comparing paleoclimatic records where different species have been measured for the isotopic composition of the calcite. The difference in habitat produces a three dimensional spatial complexity (a foraminifera living in preferred climatic conditions at a specific location, but also at a specific depth, sometimes far from the surface) but also a temporal uncertainty (foraminifers generally live for only a few weeks and their growth season may be evolving through time with climate change). While the different species habitats potentially contain a wealth of information that could be used to better understand the sequences of climate change, this has seldom been used in modeling studies, most models deriving calcite isotopic signal from surface and annual mean conditions (e.g. Roche et al., 2014). In the present work, we propose a reduced complexity approach to compute the calcite for several planktonic foraminifers from climate model simulations under pre-industrial conditions. We base our approach on simple functions describing the temperature dependence of the different species growth rates (Lombard et al., 2009) and on probability of presence based on the physical variables computed in the climate model. We present a comparison to available sediment traps and core tops data as a validation of the methodology, focusing on the possibility for future applicability towards inversion of the signal measured in oceanic sediment cores. References

  4. Use of a multi-isotope and multi-tracer approach including organic matter isotopes for quantifying nutrient contributions from agricultural vs wastewater sources

    NASA Astrophysics Data System (ADS)

    Kendall, C.; Silva, S. R.; Young, M. B.

    2013-12-01

    While nutrient isotopes are a well-established tool for quantifying nutrients inputs from agricultural vs wastewater treatment plant (WWTP) sources, we have found that combining nutrient isotopes with the C, N, and S isotopic compositions of dissolved and particulate organic matter, as part of a comprehensive multi-isotope and multi-tracer approach, is a much more diagnostic approach. The main reasons why organic matter C-N-S isotopes are a useful adjunct to studies of nutrient sources and biogeochemical processes are that the dissolved and particulate organic matter associated with (1) different kinds of animals (e.g., humans vs cows) often have distinctive isotopic compositions reflecting the different diets of the animals, and (2) the different processes associated with the different land uses (e.g., in the WWTP or associated with different crop types) often result in significant differences in the isotopic compositions of the organics. The analysis of the δ34S of particulate organic matter (POM) and dissolved organic matter (DOM) has been found to be especially useful for distinguishing and quantifying water, nutrient, and organic contributions from different land uses in aquatic systems where much of the organic matter is aquatic in origin. In such environments, the bacteria and algae incorporate S from sulfate and sulfide that is isotopically labeled by the different processes associated with different land uses. We have found that there is ~35 permil range in δ34S of POM along the river-estuary continuum in the San Joaquin/Sacramento River basin, with low values associated with sulfate reduction in the upstream wetlands and high values associated with tidal inputs of marine water into the estuary. Furthermore, rice agriculture results in relatively low δ34S values whereas WWTP effluent in the Sacramento River produces distinctly higher values than upstream of the WWTP, presumably because SO2 is used to treat chlorinated effluent. The fish living

  5. Can stable isotope mass spectrometry replace ‎radiolabelled approaches in metabolic studies?

    PubMed

    Batista Silva, Willian; Daloso, Danilo M; Fernie, Alisdair R; Nunes-Nesi, Adriano; Araújo, Wagner L

    2016-08-01

    Metabolic pathways and the key regulatory points thereof can be deduced using isotopically labelled substrates. One prerequisite is the accurate measurement of the labeling pattern of targeted metabolites. The subsequent estimation of metabolic fluxes following incubation in radiolabelled substrates has been extensively used. Radiolabelling is a sensitive approach and allows determination of total label uptake since the total radiolabel content is easy to detect. However, the incubation of cells, tissues or the whole plant in a stable isotope enriched environment and the use of either mass spectrometry or nuclear magnetic resonance techniques to determine label incorporation within specific metabolites offers the possibility to readily obtain metabolic information with higher resolution. It additionally also offers an important complement to other post-genomic strategies such as metabolite profiling providing insights into the regulation of the metabolic network and thus allowing a more thorough description of plant cellular function. Thus, although safety concerns mean that stable isotope feeding is generally preferred, the techniques are in truth highly complementary and application of both approaches in tandem currently probably provides the best route towards a comprehensive understanding of plant cellular metabolism. PMID:27297990

  6. An isotopic approach for understanding the CH3Br budget of the atmosphere

    PubMed Central

    McCauley, Sean E.; Goldstein, Allen H.; DePaolo, Donald J.

    1999-01-01

    The atmospheric budget of methyl bromide (CH3Br), an ozone-depleting gas, is highly uncertain, because it has complex sources and sinks. Although oceans, biomass burning, and industrial production are identified as the major sources, the fraction of CH3Br that is contributed by each source is not well known. A mass-balance approach that exploits differences in the carbon isotopic signature (δ13C) of CH3Br sources and sinks may provide a means of reducing uncertainties in the atmospheric budget. This approach depends on the distinctiveness of industrially produced methyl bromide. Our δ13C measurements of industrial CH3Br from the three largest manufacturers worldwide yield a weighted average of −54.4‰ relative to the Peedee Belemnite standard. This result suggests that industrial CH3Br is isotopically distinct and that the carbon isotopic composition of atmospheric CH3Br may indicate what fraction of atmospheric CH3Br is anthropogenic. PMID:10468552

  7. Seeking Hidden Glaciations in the Greenhouse World: A New Approach Using Nd Isotopes

    NASA Astrophysics Data System (ADS)

    Scher, H. D.; Bohaty, S. M.

    2009-12-01

    . Detecting short lived weathering pulses associated with ephemeral glaciations requires developing high-resolution, well correlated Nd isotope records at multiple locations and paleodepths to reconstruct Nd isotope changes through time. Broad spatial coverage of Nd isotope records is important for distinguishing between circulation changes and weathering pulses. This approach has the potential to reveal the frequency, timing, and duration of ephemeral glaciations.

  8. A tungsten isotope approach to search for meteoritic components in terrestrial impact rocks

    NASA Astrophysics Data System (ADS)

    Moynier, Frederic; Koeberl, Christian; Quitté, Ghylaine; Telouk, Philippe

    2009-08-01

    The identification of meteorite impact structures on Earth is based on two main criteria: the presence of shock-metamorphic effects in the crater rock ejecta and/or the confirmation of an extraterrestrial (meteoritic) component in breccias or melt rocks. For the latter, both high elemental abundances of siderophile elements (especially the platinum group elements) with corresponding meteoritic inter-element ratios and the osmium (Os) and chromium (Cr) isotopic signatures characteristic of meteorites have been used successfully. Inspired by earlier suggestions of a meteoritic component in Archean rocks based on tungsten (W) isotope anomalies, here we explore the possible use of 182W, which has been produced by the decay of now extinct 182Hf ( T1/2 = 8.9 Ma), as a tracer of meteoritic component in terrestrial material. Each group of meteorites has W isotopic compositions that are distinct from each other and from the terrestrial crust. 182W has already been used to try to identify the impactor at the K/T boundary by analyzing the sediments and Ni-rich spinel. In the present study, we broaden the field of investigation by choosing a different approach, namely analyzing a variety of known impact rocks. We measured the W isotope composition in four samples from different impact structures (Gardnos, Norway; Morokweng, South Africa; Vredefort, South Africa; Ries, Germany) as well as in two samples from a distal ejecta layer (K-T boundary samples from Gams, Austria, and Berwind Canyon, USA). All these samples are unambiguously impact-produced and in several of those materials a meteoritic component has unequivocally been identified by other geochemical proxies. In all these samples, the isotopic composition of W is identical with analytical error to that of the Earth's continental crust, and no 182W anomalies are present, even in the samples containing a significant (percent level) meteoritic component. Therefore, we conclude that, in contrast to the Cr or Os isotopes, W

  9. The jackknife as an approach for uncertainty assessment in gamma spectrometric measurements of uranium isotope ratios

    NASA Astrophysics Data System (ADS)

    Ramebäck, H.; Vesterlund, A.; Tovedal, A.; Nygren, U.; Wallberg, L.; Holm, E.; Ekberg, C.; Skarnemark, G.

    2010-08-01

    The jackknife as an approach for uncertainty estimation in gamma spectrometric uranium isotope ratio measurements was evaluated. Five different materials ranging from depleted uranium (DU) to high enriched uranium (HEU) were measured using gamma spectrometry. High resolution inductively coupled plasma mass spectrometry (ICP-SFMS) was used as a reference method for comparing the results obtained with the gamma spectrometric method. The relative combined uncertainty in the gamma spectrometric measurements of the 238U/ 235U isotope ratio using the jackknife was about 10-20% ( k = 2), which proved to be fit-for-purpose in order to distinguish between different uranium categories. Moreover, the enrichment of 235U in HEU could be measured with an uncertainty of 1-2%.

  10. Stable isotope approaches for tracking C cycling and function in microbial communities

    NASA Astrophysics Data System (ADS)

    Pett-Ridge, J.

    2008-12-01

    Identifying the microorganisms responsible for specific processes in C cycling remains a major challenge in environmental microbiology, one that requires integration of multiple techniques. Stable isotope probing, or SIP, has come to represent a variety of powerful approaches that allow simultaneous identification of identity and function in microbial communities. Bulk methods such as DNA/RNA-SIP and PLFA-SIP are well developed and allow tracking of a multitude of C substrates (acetate, cellulose, CH4, CO2, and plant litter) into specific microbial consumers. However, to understand the spatio-temporal context of may key C transformations and microbial interactions, new imaging technologies are needed to analyze processes and properties of macromolecule complexes, microbes, plant root cells, soil (micro)aggregates, phytoplankton and marine snow as they undergoes formation and decomposition. New and sensitive in situ approaches include NanoSIMS single cell analysis, isotope arrays, and combinations of immuno- or FISH labeling with high resolution isotope imaging. Recent work illustrates how these powerful new techniques use targeted stable isotope probing to measure biological, physical and chemical processes and can be used in soil systems to study microbial mats or rhizosphere interactions. In both terrestrial and aquatic systems, they allow us to directly link C and other nutrient metabolism at the organismal level. Lastly, these new aproaches may be of great use in the study of trophic cascades and metabolic networks. While cross-feeding is often thought of as a confounding effect in SIP-type studies, with fine scale temporal sampling and FISH-SIMS analysis, we have the opportunity trace C flows through microbial foodwebs and to their eventual fate in stabilized organic-mineral complexes.

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

    NASA Astrophysics Data System (ADS)

    Siegwolf, Rolf; Saurer, Matthias

    2016-04-01

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

  12. Figuring out the process of denitrification by stable isotope approaches - Prospects and limitations -

    NASA Astrophysics Data System (ADS)

    Stange, C. F.; Spott, O.

    2009-04-01

    Improvement in the analysis of stable isotopes, higher measurement capacity and faster and more complex analysis methods allow a more detailed insight into the complexity of N cycling in soils or sediments, in particular in the formation and emission of N2 gas. The knowledge about the site-specific N2 to N2O ratio of denitrification and perhaps other processes is important to develop sustainable land use strategies for reduction of GHG emissions. Adapted stable isotope approaches are an irreplaceable tool for process identification, process quantification and processes separation. In the last years a few of new processes were found (e.g. anammox, codenitrification) and new stable isotope approaches for quantification and processes separation were published (Wrage et al.). Source partitioning of N gas production in soils is inherently challenging, but is vital to better understand controls on the different processes, with a view to develope appropriate management practices for mitigation of harmful N gases (e.g.N2O) (Baggs, 2008). Recently dual-isotope labelling approaches (Wrage et al., 2005) and triplet 15N tracer experiments (TTE) with 15N labelling of different pools (e.g. Müller et al., 2006, Russow et al 2009) have been developed to differentiate between more than two processes. The high number of simultaneously occurring processes during soil N cycling (Hayatsu et al. 2008) limits an easy applicability of isotope approaches (Spott and Stange 2007 ;Wrage et al. 2005; Phillips and Gregg, 2003), and therefore partitioning and process quantification is often afflicted with high uncertainties (Ambus et al., 2006). Especially the heterogeneity of environmental conditions in soils caused by the soil structure is difficult to handle (e.g. homogeneously labelling a soil). Hence, spatially separated processes in combination with high turnover rates (gross production and consumption) can produce different pools of one substrate in the soil (Russow et al. 2009) and

  13. Simultaneous detection of forbidden chemical residues in milk using dual-label time-resolved reverse competitive chemiluminescent immunoassay based on amine group functionalized surface.

    PubMed

    Zhang, Dongdong; Tao, Xiaoqi; Jiang, Haiyang; Wen, Kai; Shen, Jianzhong; Cao, Xingyuan

    2014-01-01

    In this study, a sensitive dual-label time-resolved reverse competitive chemiluminescent immunoassay was developed for simultaneous detection of chloramphenicol (CAP) and clenbuterol (CLE) in milk. The strategy was performed based on the distinction of the kinetic characteristics of horseradish peroxidase (HRP) and alkaline phosphatase (ALP) in chemiluminesecence (CL) systems and different orders of magnitude in HRP CL value for CAP and ALP CL value for CLE in the chemiluminescent immunoassay. Capture antibodies were covalently bound to the amine group functionalized chemiluminescent microtiter plate (MTP) for efficient binding of detection antibodies for the enzymes labeled CAP (HRP-CAP) and CLE (ALP-CLE). The CL signals were recorded at different time points by the automatic luminometers with significant distinction in the dynamic curves. When we considered the ALP CL value (about 10(5)) of CLE as background for HRP CL signal value (about 10(7)) of CAP, there was no interaction from ALP CL background of CLE and the differentiation of CAP and CLE can be easily achieved. The 50% inhibition concentration (IC50) values of CAP and CLE in milk samples were 0.00501 µg L(-1) and 0.0128 µg L(-1), with the ranges from 0.0003 µg L(-1) to 0.0912 µg L(-1) and from 0.00385 µg L(-1) to 0.125 µg L(-1), respectively. The developed method is more sensitive and of less duration than the commercial ELISA kits, suitable for simultaneous screening of CAP and CLE. PMID:25313517

  14. Dietary plasticity of generalist and specialist ungulates in the Namibian Desert: a stable isotopes approach.

    PubMed

    Lehmann, David; Mfune, John Kazgeba Elijah; Gewers, Erick; Cloete, Johann; Brain, Conrad; Voigt, Christian Claus

    2013-01-01

    Desert ungulates live in adverse ecosystems that are particularly sensitive to degradation and global climate change. Here, we asked how two ungulate species with contrasting feeding habits, grazing gemsbok (Oryx g. gazella) and browsing springbok (Antidorcas marsupialis), respond to an increase in food availability during a pronounced rain period. We used a stable isotope approach to delineate the feeding habits of these two ungulates in the arid Kunene Region of Namibia. Our nineteen months field investigation included two time periods of drought when food availability for ungulates was lowest and an intermediate period with extreme, unusual rainfalls. We documented thirteen isotopically distinct food sources in the isotopic space of the study area. Our results indicated a relatively high dietary plasticity of gemsbok, which fed on a mixture of plants, including more than 30% of C3 plants during drought periods, but almost exclusively on C4 and CAM plant types when food was plentiful. During drought periods, the inferred gemsbok diets also consisted of up to 25% of Euphorbia damarana; an endemic CAM plant that is rich in toxic secondary plant compounds. In contrast, springbok were generalists, feeding on a higher proportion of C3 than C4/CAM plants, irrespective of environmental conditions. Our results illustrate two dietary strategies in gemsbok and springbok which enable them to survive and coexist in the hostile Kunene arid ecosystem. PMID:23977249

  15. Carbon Biogeochemistry: A Stable Isotope Approach to Trophic Dynamics in an Indian Coastal Ecosystem

    NASA Astrophysics Data System (ADS)

    Mathukumalli, B.; Alagappan, R.

    2005-12-01

    Stable isotope(δ13C & δ15N) approach was applied to understand carbon biogeochemistry and trophic dynamics in an Indian coastal mangrove wetland. The δ13C and δ15N values of potential nutrient sources (mangrove plant leaves, lichen, sediment and suspended material) and in seven species of consumers (invertebrates) were measured. The value of δ13C and δ15N isotopes of different potential nutrient sources and the consumers determine the sources of nutrients for the invertebrate consumer community of the mangrove. There is a significant variation in the stable carbon in the nutrient sources; however, δ15N signatures were not significantly different among the different potential nutrient sources. Organic matter in the sediments under the mangrove vegetation was characterized by relatively negatively fractionated and moderately high C:N ratios, indicating that mangrove derived organic matter was the principal diet source for the invertebrate consumer communities in the mangrove ecosystem. Invertebrates in the mangrove showed a wide range of δ13C signatures and are enriched relative to the mangrove leaf stable isotope values. Micro-environmental differences certainly drive the variability in the nutrient sources and consumable nature among the different regions of the ecosystem. Therefore, further research is needed to determine whether carbon assimilation is different from one zone to another.

  16. Isotopic tracing of clear water sources in an urban sewer: A combined water and dissolved sulfate stable isotope approach.

    PubMed

    Houhou, J; Lartiges, B S; France-Lanord, C; Guilmette, C; Poix, S; Mustin, C

    2010-01-01

    This paper investigates the potential of stable isotopes of both water (deltaD and deltaOH(2)O18) and dissolved sulfate (delta(34)S and deltaOSO(4)18) for determining the origin and the amount of clear waters entering an urban sewer. The dynamics of various hydrological processes that commonly occur within the sewer system such as groundwater infiltration, rainwater percolation, or stormwater release from retention basins, can be readily described using water isotope ratios. In particular, stable water isotopes indicate that the relative volumes of infiltrated groundwater and sewage remain approximately constant and independent of wastewater flow rate during the day, thus demonstrating that the usual quantification of parasitic discharge from minimal nocturnal flow measurements can lead to completely erroneous results. The isotopic signature of dissolved sulfate can also provide valuable information about the nature of water inputs to the sewage flow, but could not be used in our case to quantify the infiltrating water. Indeed, even though the microbial activity had a limited effect on the isotopic composition of dissolved sulfate at the sampling sites investigated, the dissolved sulfate concentration in sewage was regulated by the formation of barite and calcium-phosphate mineral species. Sulfate originating from urine was also detected as a source using the oxygen isotopic composition of sulfate, which suggests that deltaOSO(4)18 might find use as a urine tracer. PMID:19822346

  17. Two-Pronged Approach to Overcome Spectroscopically Interfering Organic Compounds with Isotopic Water Analysis

    NASA Astrophysics Data System (ADS)

    Saad, Nabil; Hsiao, Gregor; Chapellet-Volpini, London; Vu, Danthu

    2013-04-01

    The ability to measure the stable isotopes of hydrogen (dD) and oxygen (d18O) has become much more accessible with the advent of Cavity Ring-Down Spectroscopy (CRDS) laser optical devices. These small and inexpensive analyzers have led to a significant increase in the acquisition of data from a variety of studies in the fields of groundwater, watershed, and other water source applications. However for some samples, such as those linked to fracking, mining, and other activities where higher than normal concentrations of organic materials are to be found, optical spectroscopy may require an adaptation from current methodologies in order to ensure data confidence. That is because CRDS is able to measure all the components within a spectral region - which will include the spectral characteristics of the isotopologues of water as well as the available features from interfering organic molecules. Although, at the first level, the information from the organic material provides spectral overlaps that can perturb the isotopic ratios, a more thorough review shows that these features are a source of information that will be inherently useful. This presentation will examine the approaches developed within the past year to allow for more accurate analyses of such samples by optical methods. The first approach uses an advanced spectroscopic model to flag the presence of organic material in the sample. Signals from known interfering compounds (i.e., alcohols, ketones, aldehydes, short-chain hydrocarbons, etc.) are incorporated into the overall fit of the measured spectra used to calculate the concentration of the individual isotopes. The second approach uses physical treatment of the sample to break down the organic molecules into non-interfering species. The vaporized liquid or solid sample travels through a cartridge packed with an oxidation catalyst. The interfering organic molecules will undergo high temperature oxidation using O2 present in the air carrier gas stream prior

  18. Occurrence and origin of methane in groundwater in Alberta (Canada): Gas geochemical and isotopic approaches.

    PubMed

    Humez, P; Mayer, B; Ing, J; Nightingale, M; Becker, V; Kingston, A; Akbilgic, O; Taylor, S

    2016-01-15

    To assess potential future impacts on shallow aquifers by leakage of natural gas from unconventional energy resource development it is essential to establish a reliable baseline. Occurrence of methane in shallow groundwater in Alberta between 2006 and 2014 was assessed and was ubiquitous in 186 sampled monitoring wells. Free and dissolved gas sampling and measurement approaches yielded comparable results with low methane concentrations in shallow groundwater, but in 28 samples from 21 wells methane exceeded 10mg/L in dissolved gas and 300,000 ppmv in free gas. Methane concentrations in free and dissolved gas samples were found to increase with well depth and were especially elevated in groundwater obtained from aquifers containing coal seams and shale units. Carbon isotope ratios of methane averaged -69.7 ± 11.1‰ (n=63) in free gas and -65.6 ± 8.9‰ (n=26) in dissolved gas. δ(13)C values were not found to vary with well depth or lithology indicating that methane in Alberta groundwater was derived from a similar source. The low δ(13)C values in concert with average δ(2)HCH4 values of -289 ± 44‰ (n=45) suggest that most methane was of biogenic origin predominantly generated via CO2 reduction. This interpretation is confirmed by dryness parameters typically >500 due to only small amounts of ethane and a lack of propane in most samples. Comparison with mud gas profile carbon isotope data revealed that methane in the investigated shallow groundwater in Alberta is isotopically similar to hydrocarbon gases found in 100-250 meter depths in the WCSB and is currently not sourced from thermogenic hydrocarbon occurrences in deeper portions of the basin. The chemical and isotopic data for methane gas samples obtained from Alberta groundwater provide an excellent baseline against which potential future impact of deeper stray gases on shallow aquifers can be assessed. PMID:26476065

  19. Evaluation of the kinetic isotope effect in methylamine dehydrogenase using the wave function propagation approach

    NASA Astrophysics Data System (ADS)

    Pierdominici-Sottile, Gustavo; Palma, Juliana

    2009-09-01

    We have evaluated the kinetic isotope effect (KIE) in the proton transfer step that determines the oxidation rate of methylamine, catalyzed by the enzyme methylamine dehydrogenase. Calculations were performed with the wave function propagation (WFP) approach, recently implemented to estimate the KIE in soybean lipoxygenase-1. Two different versions of the method were applied. Both of them produced results which are close to the experimental value of 16.8 ± 0.5. The calculation required the development of a valence-bond parameterization. In the article, we describe the procedure followed to obtain these parameters, present the results of several tests employed to assess their performance and give details of the two versions of the WFP approach used to evaluate the KIE.

  20. Identification of the nitrate contamination sources of the Brusselian sands groundwater body (Belgium) using a dual-isotope approach

    NASA Astrophysics Data System (ADS)

    Mattern, Samuel; Vanclooster, Marnik

    2010-05-01

    Knowledge of the groundwater pollution source is of primary importance to define appropriate remediation strategies. Yet, the identification of the contamination sources remains a complicated task. A dual isotope approach has been used to provide information for tracing sources of nitrate in water. In this study, we used the naturally occurring stable isotopic composition of groundwater nitrate (1) to evaluate the origin of nitrate in the Brussels sands aquifer (Belgium) and (2) to study the temporal dynamics of the isotope signature of groundwater nitrate in this region. Potential N sources sampled in the region, including e.g. ammonium and nitrate mineral fertilizers, sewage and rain, had isotopic signatures that fell within the corresponding typical ranges found in literature. Some of them however deviated from the isotopic ranges corresponding to typical N sources, illustrating the impact of processes affecting the isotopic signature of the nitrate sources. During a pluri-annual sampling campaign, groundwater samples were collected at 10 moments between June 2007 and February of 2009 over 9 monitoring stations located in the western part of the study area. The isotopic data time series suggest that, most of the time, N applied on the soil has been cycled in the soil by micro-organisms before leaching to the groundwater, while the isotopic data and the high nitrate concentrations strongly suggests that nitrate of the groundwater sampled in January 2008 principally originates from mineral fertilizers. The isotopic data measured at some of the 114 monitoring stations across the study area strongly suggests that the sources of nitrate are mineral fertilizers used in agriculture and golf courses, manure leaching from unprotected stockpiles in farms, domestic gardening practices, cesspools and probably cemeteries. Isotopic data are particularly helpful when associated with other information like historical data about monitoring stations, land use, chemical parameters

  1. A Learner-Centered Spiral Knowledge Approach to Teaching Isotope Geology

    NASA Astrophysics Data System (ADS)

    Reid, M. R.

    2006-12-01

    Aided by the insights I gained by participation in the Arizona Board of Regents Tri-University Collaboration on Learner-Centered Practice, I made major changes to a graduate course in isotope geology (GLG617), including: 1) implementation of a spiral knowledge approach (e.g., Bruner, 1990; Dyar et al., 2004); 2) incorporation of more learner-centered in-class activities; and 3) more explicit emphasis on skills that I regarded as important for success in geochemistry. In the geosciences, the field of isotope geology is now an essential area of inquiry with implications for geologic timescales, climate information, tracing geochemical processes, and biological evolution, to name a few. The traditional approach to teaching isotope geology suffers from the fact that learning tends to be compartmentalized by technique/approach and one subfield (e.g., stable or radiogenic isotopes) is usually favored by appearing earlier in semester. To make learning more integrated, I employed a simplified spiral learning approach so that common principles could be revisited several times over the course of the semester and, in so doing, students' grasp of the fundamental principles could be scaffolded into greater understanding. Other learner-centered changes to the course included more explicit emphasis on helping students become comfortable with interpreting data displayed graphically and explicit emphasis on helping students give and evaluate oral presentations that rely on isotope data. I also developed a detailed grading rubric for the final paper and allowed students to have a draft of their final papers evaluated and graded (guided by Huba and Freed, 2000) A number of cooperative learning activities developed specifically for this course (19 in all) enabled me to gain a better appreciation for students' learning. Activities included pair share, round-robin, small group explorations of techniques and case studies (sometimes as introduction to, sometimes as review of material

  2. Xyloglucan undergoes interpolymeric transglycosylation during binding to the plant cell wall in vivo: evidence from 13C/3H dual labelling and isopycnic centrifugation in caesium trifluoroacetate.

    PubMed Central

    Thompson, J E; Smith, R C; Fry, S C

    1997-01-01

    Xyloglucan from the walls of Rosa cells that had been cultured on [12C]- or [13C]-glucose formed bands in caesium trifluoroacetate with mean buoyant densities of 1.575 or 1.616 g/ml respectively. Incubation of a mixture of [13C,3H]xyloglucan and [12C,1H]xyloglucan in the presence of xyloglucan endotransglycosylase (XET) activity caused the mean buoyant density of the radioactive material to decrease, indicating that interpolymeric transglycosylation could be detected in vitro. We used two 13C/3H-dual-labelling protocols to look for interpolymeric transglycosylation in vivo. In protocol A, [13C]glucose-grown Rosa cells were transferred into [12C]glucose medium 6 h after a approximately 2 h pulse of l-[1-3H]arabinose (which radiolabels the xylose residues of xyloglucan). The mean buoyant density of the wall-bound [3H]xyloglucan decreased during the following 7 days in culture. This indicates that, during or after the wall-binding of newly synthesized [12C,1H]xyloglucan, it became covalently attached to previously wall-bound [13C, 3H]xyloglucan. In protocol B, [12C]glycerol- or [12C]glucose-grown Rosa cells were transferred into [13C]glucose medium, 20 or 60 min before a approximately 2 h pulse of [3H]arabinose. The buoyant density of the earliest wall-bound [3H]xyloglucan showed that it had a 12C/13C ratio of approximately 1:1. This indicates that, during (or, implausibly, before) wall-binding, the newly synthesized [13C, 3H]xyloglucan became covalently attached to previously synthesized [12C]xyloglucan. During the following 7 days in culture, the mean buoyant density of the [3H]xyloglucan increased, showing that later-synthesized [13C,1H]xyloglucan can be covalently attached to previously wall-bound [12C,13C,3H]xyloglucan. The only known mechanism by which segments of xyloglucans could become covalently attached to each other in the cell wall is by interpolymeric transglycosylation catalysed by XET. We conclude that XET-catalysed interpolymeric transglycosylation

  3. Using micro-isotopic approaches to evaluate the origin and emplacement mechanism of the Basement Sill, Dry Valleys, Antarctica

    NASA Astrophysics Data System (ADS)

    Davidson, J. P.; Jerram, D.; Petford, N.; Marsh, B.

    2005-12-01

    Isotopic fingerprinting of mineral phases in volcanic rocks has been successfully employed recently to track magma evolution and to identify populations from different sources. Integration of this approach with textural characterisation allows chemical evolution to be integrated with physical changes (growth, nucleation, mixing). In plutonic rocks this approach has been shown to be valid, despite the potential for isotopic re-equilibration during more protracted cooling than volcanic rocks. In fact, the degree of isotopic reequilibration can be used to constrain the cooling rate of the rock, which, in turn, relates to the emplacement history. At the Rum layered mafic intrusion, NW Scotland, isotopically distinct plagioclase cores and rims suggest relatively rapid cooling (at the scale of an individual layer) of the order 0.1°C per year, consistent with sill-like emplacement. The origin of isotopic variation is consistent with growth from a progressively contaminated magma prior to transport and deposition. The Basement Sill of the Dry Valleys Complex, Antarctica, contains an opx-rich tongue claimed to be emplaced as a crystal mush into a crystal-poor magmatic envelope. Given the broadly similar dimensions and compositions of the Rum Intrusion and Basement Sill we expect to be able to use micro-isotopic analyses of cumulus plagioclase crystals in the opx tongue to a) determine whether the magmatic source is the same as the rest of the sill, b) constrain the effects of contamination during crystal growth and emplacement and c) constrain cooling pathways

  4. The oxygen-18 isotope approach for measuring aquatic metabolism in high-productivity waters

    USGS Publications Warehouse

    Tobias, C.R.; Böhlke, J.K.; Harvey, J.W.

    2007-01-01

    We examined the utility of ??18O2 measurements in estimating gross primary production (P), community respiration (R), and net metabolism (P:R) through diel cycles in a productive agricultural stream located in the midwestern U.S.A. Large diel swings in O2 (??200 ??mol L-1) were accompanied by large diel variation in ??18O2 (??10???). Simultaneous gas transfer measurements and laboratory-derived isotopic fractionation factors for O2 during respiration (??r) were used in conjunction with the diel monitoring of O2 and ??18O2 to calculate P, R, and P:R using three independent isotope-based methods. These estimates were compared to each other and against the traditional "open-channel diel O2-change" technique that lacked ??18O2. A principal advantage of the ??18O2 measurements was quantification of diel variation in R, which increased by up to 30% during the day, and the diel pattern in R was variable and not necessarily predictable from assumed temperature effects on R. The P, R, and P:R estimates calculated using the isotope-based approaches showed high sensitivity to the assumed system fractionation factor (??r). The optimum modeled ??r values (0.986-0.989) were roughly consistent with the laboratory-derived values, but larger (i.e., less fractionation) than ??r values typically reported for enzyme-limited respiration in open water environments. Because of large diel variation in O2, P:R could not be estimated by directly applying the typical steady-state solution to the O2 and 18O-O2 mass balance equations in the absence of gas transfer data. Instead, our results indicate that a modified steady-state solution (the daily mean value approach) could be used with time-averaged O2 and ??18O2 measurements to calculate P:R independent of gas transfer. This approach was applicable under specifically defined, net heterotrophic conditions. The diel cycle of increasing daytime R and decreasing nighttime R was only partially explained by temperature variation, but could be

  5. Estimating ground-water inflow to lakes in central Florida using the isotope mass-balance approach

    USGS Publications Warehouse

    Sacks, Laura A.

    2002-01-01

    The isotope mass-balance approach was used to estimate ground-water inflow to 81 lakes in the central highlands and coastal lowlands of central Florida. The study area is characterized by a subtropical climate and numerous lakes in a mantled karst terrain. Ground-water inflow was computed using both steady-state and transient formulations of the isotope mass-balance equation. More detailed data were collected from two study lakes, including climatic, hydrologic, and isotopic (hydrogen and oxygen isotope ratio) data. For one of these lakes (Lake Starr), ground-water inflow was independently computed from a water-budget study. Climatic and isotopic data collected from the two lakes were similar even though they were in different physiographic settings about 60 miles apart. Isotopic data from all of the study lakes plotted on an evaporation trend line, which had a very similar slope to the theoretical slope computed for Lake Starr. These similarities suggest that data collected from the detailed study lakes can be extrapolated to the rest of the study area. Ground-water inflow computed using the isotope mass-balance approach ranged from 0 to more than 260 inches per year (or 0 to more than 80 percent of total inflows). Steady-state and transient estimates of ground-water inflow were very similar. Computed ground-water inflow was most sensitive to uncertainty in variables used to calculate the isotopic composition of lake evaporate (isotopic compositions of lake water and atmospheric moisture and climatic variables). Transient results were particularly sensitive to changes in the isotopic composition of lake water. Uncertainty in ground-water inflow results is considerably less for lakes with higher ground-water inflow than for lakes with lower ground-water inflow. Because of these uncertainties, the isotope mass-balance approach is better used to distinguish whether ground-water inflow quantities fall within certain ranges of values, rather than for precise

  6. A quantitative approach to combine sources in stable isotope mixing models

    EPA Science Inventory

    Stable isotope mixing models, used to estimate source contributions to a mixture, typically yield highly uncertain estimates when there are many sources and relatively few isotope elements. Previously, ecologists have either accepted the uncertain contribution estimates for indiv...

  7. A Combined Stable Isotope And Machine Learning Approach To Quantify And Classify Of Nitrate Pollution Sources

    NASA Astrophysics Data System (ADS)

    Boeckx, P. F.; Xue, D.; De Baets, B.

    2011-12-01

    Stable isotope analyses of NO3- (δ15N and δ18O) are widely used to determine the sources of nitrate pollution in water. The objective of our study was (1) to quantify NO3- sources in surface water and to classify surface waters in NO3- pollution classes via a combined stable isotope and machine learning approach; and (2) to assess a decision tree model with physicochemical data for retrieving the latter classification. A logical approach has been followed: (1) 2-year monthly sampling of 30 sampling points from different river basins in Belgium, which were classified into 5 different NO3- pollution classes using experts knowledge (Agriculture (A), Agriculture with groundwater compensation (AGC), Combination of agriculture and horticulture (AH), Greenhouses in an agricultural area (G) and Households (H)); (2) estimating proportional NO3- source contribution per NO3- pollution class by applying a Bayesian isotopic mixing model (SIAR) for measured isotopic data of NO3-; (3) re-classifying the 30 sampling points into NO3- pollution classes via a k-means clustering of the SIAR outputs; and (4) building a decision tree model using physicochemical data to retrieve expert knowledge and k-means clustering classification. SIAR successfully estimated proportional contribution ranges of five potential NO3- sources: NO3- in precipitation, NO3- in fertilizer, NH4+ in fertilizer and precipitation, manure and sewage and soil N. For classes A, AGC, AH and H in winter manure and sewage were major (40 - 60%), NO3- in precipitation minor (< 10%), and the other three sources intermediate (10 - 30%) sources. For class G in winter manure and sewage was a dominant source (50%) and the other four sources contributed in an equal range (10 - 20%). The proportional source contributions shifted in summer. Manure and sewage was the dominant source (30 - 40%) for classes A and AH. For class G the source contributions of manure and sewage and NO3- in precipitation were dominant (30% each) and

  8. Estimating phreatic evaporation in irrigated areas using a stable isotope approach

    NASA Astrophysics Data System (ADS)

    Barthold, F. K.; Umirzakov, G.; Schneider, K.; Stulina, G.; Frede, H.; Breuer, L.

    2011-12-01

    Central Asia is characterized by continental arid climate conditions. Mean annual precipitation is 170 mm with a potential evapotranspiration rate of 1200 mm/a. In addition, many regions are affected by a non-sustainable use of the water resources. 90% of the water resources are used for irrigation purposes to grow e.g. cotton and wheat, especially in Uzbekistan. Large amounts of water are needed for cotton growth. Not only does the plant itself require large amounts of water but a substantial part of the water use is ascribed to the inefficient irrigation system and management. The irrigation infrastructure is old and not maintained well and irrigation management is inadequate. Groundwater level rise has been observed in irrigated areas as a result of the inefficient irrigation practices. Capillary raised groundwater is particularly prone to evaporation as it gets closer to the soil surface. The general objective of this study is to quantify the amount of groundwater (or phreatic) evaporation that is due to groundwater table rise on irrigated fields. In this study, we present an approach where we are using stable isotopes of water to estimate phreatic evaporation on irrigated fields. Our specific objective is to estimate phreatic evaporation (Ep) in relation to the groundwater level and varying soil types (sandy, loamy and clay loamy). We chose a stable water isotopes approach to estimate Ep. For this purpose, soil samples along a depth profile were sampled on sites with different groundwater levels and soil types. Samples were taken in 10 cm increments down to the groundwater level. Soil water was extracted using a cryogenic vacuum distillation and the extracted soil water was analyzed for its composition of stable water isotopes, δD and δ18O, using a Liquid Water Isotope Analyzer (Los Gatos Research, Inc.). Ep was calculated by fitting an exponential function to the experimental isotope soil profile. Our results show that in sandy and loamy soils, enrichment

  9. Conformational effect of dicyclo-hexano-18-crown-6 on isotopic fractionation of zinc: DFT approach

    SciTech Connect

    Boda, A.; Singha Deb, A. K.; Ali, Sk. M.; Shenoy, K. T.; Ghosh, S. K.

    2014-04-24

    Generalized gradient approximated BP86 density functional employing triple zeta valence plus polarization (TZVP) basis set has been used to compute the reduced partition function ratio and isotopic separation factor for zinc isotopes. The isotopic separation factor was found to be in good agreement with the experimental results. The isotopic separation factor was found to depend on the conformation of the crown ether ligand. The trans-trans conformation shows the highest fractionation compared to cis-cis conformer. The present theoretical results can thus be used to plan the isotope separation experiments.

  10. Identifying diffused nitrate sources in a stream in an agricultural field using a dual isotopic approach.

    PubMed

    Ding, Jingtao; Xi, Beidou; Gao, Rutai; He, Liansheng; Liu, Hongliang; Dai, Xuanli; Yu, Yijun

    2014-06-15

    Nitrate (NO3(-)) pollution is a severe problem in aquatic systems in Taihu Lake Basin in China. A dual isotope approach (δ(15)NNO3(-) and δ(18)ONO3(-)) was applied to identify diffused NO3(-) inputs in a stream in an agricultural field at the basin in 2013. The site-specific isotopic characteristics of five NO3(-) sources (atmospheric deposition, AD; NO3(-) derived from soil organic matter nitrification, NS; NO3(-) derived from chemical fertilizer nitrification, NF; groundwater, GW; and manure and sewage, M&S) were identified. NO3(-) concentrations in the stream during the rainy season [mean±standard deviation (SD)=2.5±0.4mg/L] were lower than those during the dry season (mean±SD=4.0±0.5mg/L), whereas the δ(18)ONO3(-) values during the rainy season (mean±SD=+12.3±3.6‰) were higher than those during the dry season (mean±SD=+0.9±1.9‰). Both chemical and isotopic characteristics indicated that mixing with atmospheric NO3(-) resulted in the high δ(18)O values during the rainy season, whereas NS and M&S were the dominant NO3(-) sources during the dry season. A Bayesian model was used to determine the contribution of each NO3(-) source to total stream NO3(-). Results showed that reduced N nitrification in soil zones (including soil organic matter and fertilizer) was the main NO3(-) source throughout the year. M&S contributed more NO3(-) during the dry season (22.4%) than during the rainy season (17.8%). AD generated substantial amounts of NO3(-) in May (18.4%), June (29.8%), and July (24.5%). With the assessment of temporal variation of diffused NO3(-) sources in agricultural field, improved agricultural management practices can be implemented to protect the water resource and avoid further water quality deterioration in Taihu Lake Basin. PMID:24686140

  11. Ecophysiological responses of trees to long- term N deposition: a multi isotopes approach

    NASA Astrophysics Data System (ADS)

    Battipaglia, G.; Lubritto, C.; Altieri, S.; Marzaioli, F.; Cherubini, P.; Cotrufo, M. F.

    2009-04-01

    Anthropogenic emissions of nitrogen compounds, principally derived from the burning of fossil fuels, have lead to regional changes in atmospheric and precipitation chemistry. The fate and environmental consequences of these changes on ecosystems functions and on forest growth has attracted considerable research. The d15N measurements have been used successfully for detecting changes in N deposition and incorporation of atmospheric N into leaves (Siegwolf et al,2001) and tree rings (Poulson et al.,1995; Saurer et al.,2004, Guerrieri et al.2009). We show main results arising from a study of mature Pinus pinea individuals exposed to large amount of traffic exhaust for 20 years. Specifically, we examined the time-related trend in the growth residuals through dendrochronological analysis and C and N isotopes. A consistent decrease in the ring width starting from 1980 with a slight increase in δ13C value has been found as a consequence of environmental stress event. More over the effect of the fossil source 14C dilution on the atmospheric bomb enriched background has been detected in tree rings over the last decades, as a consequence of the increase in uptaking of traffic exhaust. The great variability in δ15N values of tree rings with time underlines the difficulties we encountered in using N as an environmental tool and open new questions and research avenues. Guerrieri M.R., Siegwolf R.T.W., Saurer M., Jäggi M., Cherubini., Ripullone F., Borghetti M., (2009)"Impact of different nitrogen emission sources on tree physiology as assessed by a triple stable isotope approach" Atmospheric Environment 43:410-418 Pearson J., Wellis D.M., Seller K.J., Bennet A., Soares A., Woodall J., Ingroulle M.J. (2000). Traffic exposure increases natural 15N and heavy metal concentrations in mosses. New Phytologist 147: 317-326. Siegwolf R.T.W., Matyssek R., Saurer M., Maurer S., Günthardt-Georg M.S., Schmutz P. and Bucher J.B. "Stable isotope analysis reveals differential effects of

  12. Novel Approach for High-Throughput Metabolic Screening of Whole Plants by Stable Isotopes.

    PubMed

    Dersch, Lisa Maria; Beckers, Veronique; Rasch, Detlev; Melzer, Guido; Bolten, Christoph; Kiep, Katina; Becker, Horst; Bläsing, Oliver Ernst; Fuchs, Regine; Ehrhardt, Thomas; Wittmann, Christoph

    2016-05-01

    Here, we demonstrate whole-plant metabolic profiling by stable isotope labeling and combustion isotope-ratio mass spectrometry for precise quantification of assimilation, translocation, and molecular reallocation of (13)CO2 and (15)NH4NO3 The technology was applied to rice (Oryza sativa) plants at different growth stages. For adult plants, (13)CO2 labeling revealed enhanced carbon assimilation of the flag leaf from flowering to late grain-filling stage, linked to efficient translocation into the panicle. Simultaneous (13)CO2 and (15)NH4NO3 labeling with hydroponically grown seedlings was used to quantify the relative distribution of carbon and nitrogen. Two hours after labeling, assimilated carbon was mainly retained in the shoot (69%), whereas 7% entered the root and 24% was respired. Nitrogen, taken up via the root, was largely translocated into the shoot (85%). Salt-stressed seedlings showed decreased uptake and translocation of nitrogen (69%), whereas carbon metabolism was unaffected. Coupled to a gas chromatograph, labeling analysis provided enrichment of proteinogenic amino acids. This revealed significant protein synthesis in the panicle of adult plants, whereas protein biosynthesis in adult leaves was 8-fold lower than that in seedling shoots. Generally, amino acid enrichment was similar among biosynthetic families and allowed us to infer labeling dynamics of their precursors. On this basis, early and strong (13)C enrichment of Embden-Meyerhof-Parnas pathway and pentose phosphate pathway intermediates indicated high activity of these routes. Applied to mode-of-action analysis of herbicides, the approach showed severe disturbance in the synthesis of branched-chain amino acids upon treatment with imazapyr. The established technology displays a breakthrough for quantitative high-throughput plant metabolic phenotyping. PMID:26966172

  13. Kinetic oxygen isotope effects during dissimilatory sulfate reduction: A combined theoretical and experimental approach

    NASA Astrophysics Data System (ADS)

    Turchyn, Alexandra V.; Brüchert, Volker; Lyons, Timothy W.; Engel, Gregory S.; Balci, Nurgul; Schrag, Daniel P.; Brunner, Benjamin

    2010-04-01

    Kinetic isotope effects related to the breaking of chemical bonds drive sulfur isotope fractionation during dissimilatory sulfate reduction (DSR), whereas oxygen isotope fractionation during DSR is dominated by exchange between intercellular sulfur intermediates and water. We use a simplified biochemical model for DSR to explore how a kinetic oxygen isotope effect may be expressed. We then explore these relationships in light of evolving sulfur and oxygen isotope compositions (δ 34S SO4 and δ 18O SO4) during batch culture growth of twelve strains of sulfate-reducing bacteria. Cultured under conditions to optimize growth and with identical δ 18O H2O and initial δ 18O SO4, all strains show 34S enrichment, whereas only six strains show significant 18O enrichment. The remaining six show no (or minimal) change in δ 18O SO4 over the growth of the bacteria. We use these experimental and theoretical results to address three questions: (i) which sulfur intermediates exchange oxygen isotopes with water, (ii) what is the kinetic oxygen isotope effect related to the reduction of adenosine phosphosulfate (APS) to sulfite (SO 32-), (iii) does a kinetic oxygen isotope effect impact the apparent oxygen isotope equilibrium values? We conclude that oxygen isotope exchange between water and a sulfur intermediate likely occurs downstream of APS and that our data constrain the kinetic oxygen isotope fractionation for the reduction of APS to sulfite to be smaller than 4‰. This small oxygen isotope effect impacts the apparent oxygen isotope equilibrium as controlled by the extent to which APS reduction is rate-limiting.

  14. Phosphoprotein Isotope-Coded Solid-Phase Tag Approach for Enrichment and Quantitative Analysis of Phosphopeptides from Complex Mixtures

    SciTech Connect

    Qian, Weijun ); Goshe, Michael B.; Camp, David G. ); Yu, Li-Rong ); Tang, Keqi ); Smith, Richard D. )

    2003-10-15

    Many cellular processes are regulated by reversible protein phosphorylation and the ability to identify and quantify phosphoproteins from proteomes is essential for gaining a better understanding of these dynamic cellular processes. However, a sensitive, efficient and global method capable of addressing the phosphoproteome has yet to be developed. Here we describe an improved stable-isotope labeling method using a Phosphoprotein Isotope-coded Solid-phase Tag (PhIST) for isolating and measuring the relative abundance of phosphorylated peptides from complex peptide mixtures resulting from the enzymatic digestion of extracted proteins. The PhIST approach is an extension of the previously reported Phosphoprotein Isotope-coded Affinity Tag (PhIAT)approach developed by our laboratory1-2, where the O-phosphate moiety on phosphoseryl or phosphothreonyl residues were derivatized by hydroxide ion-medated B-elimination followed by the addition of 1,2-ethanedithiol (EDT). Instead of using the biotin affinity tag, peptides containing the EDT moiety were captured and labeled in one step using isotope-coded solid-phase reagents containing either light (12C6, 14N) or heavy (13C6, 15N) stable isotopes. The captured peptides labeled with the isotope-coded tags were released from the solid-phase support by UV photocleavage and analyzed by capillary LC-MS/MS. The efficiency and sensitivity of the PhIST labeling approach for identification of phosphopeptides from mixtures was demonstrated using casein phosphoproteins. Its utility for proteomic applications is demonstrated by the labeling of soluble proteins from human breast cancer cell line.

  15. Investigation of isotope effects with the nuclear-electronic orbital approach.

    PubMed

    Reyes, Andrés; Pak, Michael V; Hammes-Schiffer, Sharon

    2005-08-01

    This paper addresses fundamental issues that arise in the application of the nuclear-electronic orbital (NEO) approach to systems with equivalent quantum nuclei. Our analysis illustrates that Hartree-Fock nuclear wave functions do not provide physically reasonable descriptions of systems comprised of equivalent low-spin fermions or equivalent bosons. The physical basis for this breakdown is that the ionic terms dominate due to the localized nature of the nuclear orbitals. Multi-configurational wave functions that include only covalent terms provide physically reasonable descriptions of these types of systems. The application of the NEO approach to a variety of chemical systems is presented to elucidate the isotope effects on the geometries and electronic wave functions. Deuteration of hydrogen halides, water, ammonia, and hydronium ion decreases the bond length and the magnitude of negative partial atomic charge on the heavy atom. These results are consistent with experimental spectroscopic data. Deuteration at the beta position for formate anion and a series of amines increases the magnitude of negative partial atomic charge on the protonation site for the unprotonated species. This observation is consistent with the experimentally observed increase in basicity upon deuteration at the beta position for carboxylic acids and amines. PMID:16122297

  16. A stable isotope approach and its application for identifying nitrate source and transformation process in water.

    PubMed

    Xu, Shiguo; Kang, Pingping; Sun, Ya

    2016-01-01

    Nitrate contamination of water is a worldwide environmental problem. Recent studies have demonstrated that the nitrogen (N) and oxygen (O) isotopes of nitrate (NO3(-)) can be used to trace nitrogen dynamics including identifying nitrate sources and nitrogen transformation processes. This paper analyzes the current state of identifying nitrate sources and nitrogen transformation processes using N and O isotopes of nitrate. With regard to nitrate sources, δ(15)N-NO3(-) and δ(18)O-NO3(-) values typically vary between sources, allowing the sources to be isotopically fingerprinted. δ(15)N-NO3(-) is often effective at tracing NO(-)3 sources from areas with different land use. δ(18)O-NO3(-) is more useful to identify NO3(-) from atmospheric sources. Isotopic data can be combined with statistical mixing models to quantify the relative contributions of NO3(-) from multiple delineated sources. With regard to N transformation processes, N and O isotopes of nitrate can be used to decipher the degree of nitrogen transformation by such processes as nitrification, assimilation, and denitrification. In some cases, however, isotopic fractionation may alter the isotopic fingerprint associated with the delineated NO3(-) source(s). This problem may be addressed by combining the N and O isotopic data with other types of, including the concentration of selected conservative elements, e.g., chloride (Cl(-)), boron isotope (δ(11)B), and sulfur isotope (δ(35)S) data. Future studies should focus on improving stable isotope mixing models and furthering our understanding of isotopic fractionation by conducting laboratory and field experiments in different environments. PMID:26541149

  17. Quantifying groundwater dependence of a sub-polar lake cluster in Finland using an isotope mass balance approach

    NASA Astrophysics Data System (ADS)

    Isokangas, E.; Rozanski, K.; Rossi, P. M.; Ronkanen, A.-K.; Kløve, B.

    2015-03-01

    A stable isotope study of 67 kettle lakes and ponds situated on an esker aquifer (90 km2) in northern Finland was carried out to determine the role and extent of groundwater inflow in groundwater-dependent lakes. Distinct seasonal fluctuations in the δ18O and δ2H values of lakes are the result of seasonal ice cover prohibiting evaporation during the winter. An iterative isotope mass balance approach was used to calculate the inflow-to-evaporation ratios (ITOT/E) of all 67 lakes during the summer of 2013 when the isotopic compositions of the lakes were approaching a steady-state. The balance calculations were carried out independently for 2H and 18O data. Since evaporation rates were derived independently of any mass balance considerations, it was possible to determine the total inflow (ITOT) and mean turnover time (MTT) of the lakes. Furthermore, the groundwater seepage rates to all studied lakes were calculated. A quantitative measure was introduced for the dependence of a lake on groundwater (G index) that is defined as the percentage contribution of groundwater inflow to the total inflow of water to the given lake. The G index values of the lakes studied ranged from ca. 39 to 98%, revealing generally large groundwater dependency among the studied lakes. This study shows the effectiveness of applying an isotope mass balance approach to quantify the groundwater reliance of lakes situated in a relatively small area with similar climatic conditions.

  18. Determination of the origin of groundwater nitrate at an air weapons range using the dual isotope approach

    NASA Astrophysics Data System (ADS)

    Bordeleau, Geneviève; Savard, Martine M.; Martel, Richard; Ampleman, Guy; Thiboutot, Sonia

    2008-06-01

    Nitrate is one of the most common contaminants in shallow groundwater, and many sources may contribute to the nitrate load within an aquifer. Groundwater nitrate plumes have been detected at several ammunition production sites. However, the presence of multiple potential sources and the lack of existing isotopic data concerning explosive degradation-induced nitrate constitute a limitation when it comes to linking both types of contaminants. On military training ranges, high nitrate concentrations in groundwater were reported for the first time as part of the hydrogeological characterization of the Cold Lake Air Weapons Range (CLAWR), Alberta, Canada. Explosives degradation is thought to be the main source of nitrate contamination at CLAWR, as no other major source is present. Isotopic analyses of N and O in nitrate were performed on groundwater samples from the unconfined and confined aquifers; the dual isotopic analysis approach was used in order to increase the chances of identifying the source of nitrate. The isotopic ratios for the groundwater samples with low nitrate concentration suggested a natural origin with a strong contribution of anthropogenic atmospheric NO x. For the samples with nitrate concentration above the expected background level the isotopic ratios did not correspond to any source documented in the literature. Dissolved RDX samples were degraded in the laboratory and results showed that all reproduced degradation processes released nitrate with a strong fractionation. Laboratory isotopic values for RDX-derived NO 3- produced a trend of high δ18O-low δ15N to low δ18O-high δ15N, and groundwater samples with nitrate concentrations above the expected background level appeared along this trend. Our results thus point toward a characteristic field of isotopic ratios for nitrate being derived from the degradation of RDX.

  19. Determination of the origin of groundwater nitrate at an air weapons range using the dual isotope approach.

    PubMed

    Bordeleau, Geneviève; Savard, Martine M; Martel, Richard; Ampleman, Guy; Thiboutot, Sonia

    2008-06-01

    Nitrate is one of the most common contaminants in shallow groundwater, and many sources may contribute to the nitrate load within an aquifer. Groundwater nitrate plumes have been detected at several ammunition production sites. However, the presence of multiple potential sources and the lack of existing isotopic data concerning explosive degradation-induced nitrate constitute a limitation when it comes to linking both types of contaminants. On military training ranges, high nitrate concentrations in groundwater were reported for the first time as part of the hydrogeological characterization of the Cold Lake Air Weapons Range (CLAWR), Alberta, Canada. Explosives degradation is thought to be the main source of nitrate contamination at CLAWR, as no other major source is present. Isotopic analyses of N and O in nitrate were performed on groundwater samples from the unconfined and confined aquifers; the dual isotopic analysis approach was used in order to increase the chances of identifying the source of nitrate. The isotopic ratios for the groundwater samples with low nitrate concentration suggested a natural origin with a strong contribution of anthropogenic atmospheric NOx. For the samples with nitrate concentration above the expected background level the isotopic ratios did not correspond to any source documented in the literature. Dissolved RDX samples were degraded in the laboratory and results showed that all reproduced degradation processes released nitrate with a strong fractionation. Laboratory isotopic values for RDX-derived NO(3)(-) produced a trend of high delta(18)O-low delta(15)N to low delta(18)O-high delta(15)N, and groundwater samples with nitrate concentrations above the expected background level appeared along this trend. Our results thus point toward a characteristic field of isotopic ratios for nitrate being derived from the degradation of RDX. PMID:18499297

  20. Quantifying groundwater dependence of a sub-polar lake cluster in Finland using an isotope mass balance approach

    NASA Astrophysics Data System (ADS)

    Isokangas, E.; Rozanski, K.; Rossi, P. M.; Ronkanen, A.-K.; Kløve, B.

    2014-08-01

    A stable isotope study of 67 kettle lakes and ponds situated on an esker aquifer (90 km2) in northern Finland was carried out in the summer of 2013 to determine the role of groundwater inflow in groundwater-dependent lakes. Distinct seasonal fluctuations in the δ18O and δ2H values of lakes are the result of seasonal ice cover prohibiting evaporation during the winter. An isotope mass balance approach was used to calculate the inflow-to-evaporation ratios (ITOT/E) of all 67 lakes during the summer of 2013 when the isotopic compositions of the lakes were approaching a steady-state. The normalised relative humidity needed in this approach came from assuming a terminal lake situation for one of the lakes showing the highest isotope enrichment. Since evaporation rates were derived independently of any mass balance considerations, it was possible to determine the total inflow (ITOT) and mean turnover time (MTT) of the lakes. Furthermore, the groundwater seepage rates of those lakes revealing no visible surface inflow were calculated. Here, a quantitative measure was introduced for the dependence of a lake on groundwater (G index) that is defined as the percentage contribution of groundwater inflow to the total inflow of water to the given lake. The G index values of the lakes studied ranged from 27.8-95.0%, revealing large differences in groundwater dependency among the lakes. This study shows the effectiveness of applying an isotope mass balance approach to quantify the groundwater reliance of lakes situated in a relatively small area with similar climatic conditions.

  1. What is the main food source of the shipworm (Teredo navalis)? A stable isotope approach

    NASA Astrophysics Data System (ADS)

    Paalvast, Peter; van der Velde, Gerard

    2013-07-01

    Stable isotope analysis of soft bodies of the shipworm Teredo navalis demonstrated that this species is mainly feeding on seston by filter feeding in contrast to wood consumption. T. navalis showed similar stable isotope values (δ13C, δ15N) as Mytilus edulis and Crassostrea gigas, which species were attached to the wood instead of boring into.

  2. Hydrogeochemical, multiple isotopic approaches to investigate seawater mixing of groundwater in volcanic Jeju Island, Korea

    NASA Astrophysics Data System (ADS)

    Koh, E. H.; Kaown, D.; Lee, S. H.; Lee, K. K.

    2014-12-01

    Groundwater is a sole resource for water supply in Jeju Island which is composed of various formations of porous volcanic rocks. Therefore, preservation of the groundwater resource is an essential issue. Due to its geological features of the island, seawater has been intruded landward, mainly in the eastern region, which restricts groundwater use in the area. In the western region, severe nitrate contaminations of groundwater have been occurred by heavily performed agricultural activities, and moreover deterioration of groundwater quality by seawater intrusion has been observed in recent years. In this study, to delineate the mixing process related to seawater intrusion into groundwater from Gosan (western region) and Pyoseon (eastern region) of Jeju Island, hydrogeochemical and multiple isotopic approaches were applied. Also, fractionation ratios of each factors (fresh groundwater, nitrate contaminated groundwater, and seawater) which affect the groundwater quality from the study areas were estimated by using the MIX_PROGRAM. The effect of seawater was observed at the groundwater wells located inland up to 1.5 km from the coast and showed to be enlarged landward during a dry season. The fractionation ratios of seawater had the minor range (0.1~1.2%) for the Pyoseon area and 0.4~3.7% of seawater was mixed with fresh groundwater in the Gosan area. Differences in hydrogeological properties between Gosan and Pyoseon areas made dissimilar occurrences of seawater mixing into groundwater in the island.

  3. An isotopic dilution approach for 1,3-butadiene tailpipe emissions and ambient air monitoring.

    PubMed

    Riservato, Manuela; Rolla, Antonio; Davoli, Enrico

    2004-01-01

    An isotopic dilution approach for 1,3-butadiene analysis in gaseous samples is presented. The methodology is based on active sampling on sorbent tubes and subsequent analysis by thermal desorption into a gas chromatography/mass spectrometry system. By adding a perdeuterated internal standard onto the sorbent tubes before sampling, and using mass spectrometric detection, the methodology gives high accuracy for this unstable analyte. The method has been used to monitor 1,3-butadiene ambient air concentrations in a residential area in proximity to a heavy-traffic roadway over a one-week period, for comparison with other traffic-related pollutants analysed by standard procedures. It has also been used to determine tailpipe emissions of two vehicles by standard emission testing procedures in a dynamometer. These vehicles were chosen as examples of low- and high-end emission rate vehicles, i.e., an old no-catalytic converter Otto engine and a new direct-injection diesel engine with catalytic converter. Exhaust gas emissions were 0.052 and 35.85 mg/km, reflecting differences in fuel, engine design, age, and presence (or not) of a catalytic abatement system. The ambient air results showed a weekly average concentration of 1,3-butadiene of 0.53 microg/m(3). PMID:14966846

  4. An Approach for Validating Actinide and Fission Product Burnup Credit Criticality Safety Analyses-Isotopic Composition Predictions

    SciTech Connect

    Radulescu, Georgeta; Gauld, Ian C; Ilas, Germina; Wagner, John C

    2011-01-01

    The expanded use of burnup credit in the United States (U.S.) for storage and transport casks, particularly in the acceptance of credit for fission products, has been constrained by the availability of experimental fission product data to support code validation. The U.S. Nuclear Regulatory Commission (NRC) staff has noted that the rationale for restricting the Interim Staff Guidance on burnup credit for storage and transportation casks (ISG-8) to actinide-only is based largely on the lack of clear, definitive experiments that can be used to estimate the bias and uncertainty for computational analyses associated with using burnup credit. To address the issues of burnup credit criticality validation, the NRC initiated a project with the Oak Ridge National Laboratory to (1) develop and establish a technically sound validation approach for commercial spent nuclear fuel (SNF) criticality safety evaluations based on best-available data and methods and (2) apply the approach for representative SNF storage and transport configurations/conditions to demonstrate its usage and applicability, as well as to provide reference bias results. The purpose of this paper is to describe the isotopic composition (depletion) validation approach and resulting observations and recommendations. Validation of the criticality calculations is addressed in a companion paper at this conference. For isotopic composition validation, the approach is to determine burnup-dependent bias and uncertainty in the effective neutron multiplication factor (keff) due to bias and uncertainty in isotopic predictions, via comparisons of isotopic composition predictions (calculated) and measured isotopic compositions from destructive radiochemical assay utilizing as much assay data as is available, and a best-estimate Monte Carlo based method. This paper (1) provides a detailed description of the burnup credit isotopic validation approach and its technical bases, (2) describes the application of the approach for

  5. Nekton migration and feeding location in a coastal area - A stable isotope approach

    NASA Astrophysics Data System (ADS)

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

    2011-03-01

    Stable isotope analysis was used to investigate nekton movements and feeding location in a coastal area adjacent to a major European river, the Tagus, Portugal. Particulate organic matter isotopic signatures presented a gradient from the river towards the sea. Phytoplankton, zooplankton, polychaetes and the crab, Polybius henslowii, provided evidence of the incorporation of terrestrial organic matter into the lower levels of the food web, reflecting local isotopic signatures. Two fish species reflected the coastal isotopic gradient in δ13C, Diplodus vulgaris and Arnoglossus imperialis and the latter also presented isotopic differerences among the sites for δ15N. Alloteuthis subulata, Trisopterus luscus and Callionymus lyra were isotopicaly distinct among sites for δ15N. An increase of δ15N with length was detected for T. luscus and C. lyra, possibly showing ontogenic trophic level changes. Since A. subulata did not present differences in length and still showed isotopic distinction for δ15N, among areas, it was concluded that local biogeochemical factors may also have an influence. Diplodus bellottii and Dicologlossa cuneata did not reflect any isotopic signature reflecting their wide migration and feeding across the coastal area. Central isotopic ranges, defined as the site mean values for δ13C and δ15N ± 1‰ were determined for each species and site and those deviating from these were considered transient individuals. Central isotopic ranges accounted for 87% of A. imperialis, 80% of A. subulata, 77% of T. luscus, 67% of C. lyra and 50% of D. vulgaris. The number of individuals within each central isotopic range was surprisingly high for an open coastal area and comparable to those of more structured environments.

  6. Development of a combined isotopic and mass-balance approach to determine dissolved organic carbon sources in eutrophic reservoirs.

    PubMed

    Pierson-Wickmann, Anne-Catherine; Gruau, Gérard; Jardé, Emilie; Gaury, Nicolas; Brient, Luc; Lengronne, Marion; Crocq, André; Helle, Daniel; Lambert, Thibault

    2011-04-01

    A combined mass-balance and stable isotope approach was set up to identify and quantify dissolved organic carbon (DOC) sources in a DOC-rich (9mgL(-1)) eutrophic reservoir located in Western France and used for drinking water supply (so-called Rophemel reservoir). The mass-balance approach consisted in measuring the flux of allochthonous DOC on a daily basis, and in comparing it with the effective (measured) DOC concentration of the reservoir. The isotopic approach consisted, for its part, in measuring the carbon isotope ratios (δ(13)C values) of both allochthonous and autochthonous DOC sources, and comparing these values with the δ(13)C values of the reservoir DOC. Results from both approaches were consistent pointing out for a DOC of 100% allochthonous origin. In particular, the δ(13)C values of the DOC recovered in the reservoir (-28.5±0.2‰; n=22) during the algal bloom season (May-September) showed no trace of an autochthonous contribution (δ(13)C in algae=-30.1±0.3‰; n=2) being indistinguishable from the δ(13)C values of allochthonous DOC from inflowing rivers (-28.6±0.1‰; n=8). These results demonstrate that eutrophication is not responsible for the high DOC concentrations observed in the Rophemel reservoir and that limiting eutrophication of this reservoir will not reduce the potential formation of disinfection by-products during water treatment. The methodology developed in this study based on a complementary isotopic and mass-balance approach provides a powerful tool, suitable to identify and quantify DOC sources in eutrophic, DOC-contaminated reservoirs. PMID:21190712

  7. Multi-isotope approach: a tool to better constrain both sources and processes affecting NO3 pollution in watersheds

    NASA Astrophysics Data System (ADS)

    Widory, D.

    2006-12-01

    Nitrate is one of the major pollutants of drinking water resources worldwide. Recent European directives reduced inputs from intensive agriculture, but in most places NO3 levels are approaching the potable limit of 50 mg.l-1 in groundwater. Determining the source(s) of contamination in groundwater is an important first step for improving its quality by emission control. It is with this aim that we review here the benefit of using a multi- isotope approach (d15N, d180, d11B and 87Sr/86Sr), in addition to conventional hydrogeological analysis, to both constrain the watersheds hydrology and trace the origin of their NO3 pollution. Watersheds presented here include both fractured bedrock and alluvial (subsurface and deep) hydrogeological contexts. The strontium budget in watersheds is mainly controlled by the water-rock interactions (human inputs usually represents negligible fluxes). With the example of the Allier river (Central France), we show that, even on a very small watershed, the main water flows can usually be determined by the use of the 87Sr/86Sr ratios, thus helping understanding the hydrology controlling pollution processes. The characterisation of the different usual nitrate sources of pollution in groundwater (mineral fertilisers, wastewater and animals manure) shows that they can clearly be discriminated using isotopes. The isotopic composition of the dissolved nitrogen species has been used extensively to better constrain the sources and fate of nitrate in groundwater. The possibility of quantifying both origin and secondary processes affecting N concentrations by means of a single tracer appears more limited however. Nitrogen cannot be considered conservative because it is biologically modified through nitrification and denitrification reactions, both during infiltration of the water and in the groundwater body, causing isotopic fractionation that modifies the d15N-n signatures of the dissolved N species. Discriminating multiple NO3 sources by their N

  8. Partitioning net ecosystem exchange of CO2: A comparison of a Bayesian/isotope approach to environmental regression methods

    NASA Astrophysics Data System (ADS)

    Zobitz, J. M.; Burns, S. P.; OgéE, J.; Reichstein, M.; Bowling, D. R.

    2007-09-01

    Separation of the net ecosystem exchange of CO2 (F) into its component fluxes of net photosynthesis (FA) and nonfoliar respiration (FR) is important in understanding the physical and environmental controls on these fluxes, and how these fluxes may respond to environmental change. In this paper, we evaluate a partitioning method based on a combination of stable isotopes of CO2 and Bayesian optimization in the context of partitioning methods based on regressions with environmental variables. We combined high-resolution measurements of stable carbon isotopes of CO2, ecosystem fluxes, and meteorological variables with a Bayesian parameter optimization approach to estimate FA and FR in a subalpine forest in Colorado, United States, over the course of 104 days during summer 2003. Results were generally in agreement with the independent environmental regression methods of Reichstein et al. (2005a) and Yi et al. (2004). Half-hourly posterior parameter estimates of FA and FR derived from the Bayesian/isotopic method showed a strong diurnal pattern in both, consistent with established gross photosynthesis (GEE) and total ecosystem respiration (TER) relationships. Isotope-derived FA was functionally dependent on light, but FR exhibited the expected temperature dependence only when the prior estimates for FR were temperature-based. Examination of the posterior correlation matrix revealed that the available data were insufficient to independently resolve all the Bayesian-estimated parameters in our model. This could be due to a small isotopic disequilibrium (?) between FA and FR, poor characterization of whole-canopy photosynthetic discrimination or the isotopic flux (isoflux, analogous to net ecosystem exchange of 13CO2). The positive sign of ? indicates that FA was more enriched in 13C than FR. Possible reasons for this are discussed in the context of recent literature.

  9. Source apportionment of methane using a triple isotope approach - Method development and application in the Baltic Sea

    NASA Astrophysics Data System (ADS)

    Steinbach, Julia; Holmstrand, Henry; Semiletov, Igor; Shakhova, Natalia; Shcherbakova, Kseniia; Kosmach, Denis; Sapart, Célia J.; Gustafsson, Örjan

    2015-04-01

    We present a method for measurements of the stable and radiocarbon isotope systems of methane in seawater and sediments. The triple isotope characterization of methane is useful in distinguishing different sources and for improving our understanding of biogeochemical processes affecting methane in the water column. D14C-CH4 is an especially powerful addition to stable isotope analyses in distinguishing between thermogenic and biogenic origins of the methane. Such measurements require large sample sizes, due to low natural abundance of the radiocarbon in CH4. Our system for sample collection, methane extraction and purification builds on the approach by Kessler and Reeburgh (Limn. & Ocean. Meth., 2005). An in-field system extracts methane from 30 -120 l water or 1-2 l sediment (depending on the in-situ methane concentration) by purging the samples with Helium to transfer the dissolved methane to the headspace and circulating it through cryogenically cooled absorbent traps where methane is collected. The in-field preparation eliminates the risks of storage and transport of large seawater quantities and subsequent leakage of sample gas as well as ongoing microbial processes and chemical reactions that may alter the sample composition. In the subsequent shore-based treatment, a laboratory system is used to purify and combust the collected CH4 to AMS-amenable CO2. Subsamples from the methane traps are analyzed for stable isotopes and compared to stable isotope measurements directly measured from small water samples taken in parallel, to correct for any potential fractionation occurring during this process. The system has been successfully tested and used on several shorter shipboard expeditions in the Baltic Sea and on a long summer expedition across the Arctic Ocean. Here we present the details of the method and testing, as well as first triple isotope field data from two cruises to the Landsort Deep area in the Central Baltic Sea.

  10. Theoretical and Experimental Approaches to Understanding the Anomalous Distribution of Oxygen Isotopes in the Solar System

    NASA Astrophysics Data System (ADS)

    Dominguez, Gerardo; Christensen, Elizabeth; Boyer, Charisa; Park, Manesseh; Benitez, Ezra; Nunn, Morgan; Thiemens, Mark H.; Jackson, Terri

    2016-06-01

    Decades of careful laboratory analysis of primitive meteorites have revealed an intriguing and unexplained pattern in the distribution of oxygen isotopes in the solar system. With the recent analysis of solar wind oxygen by NASA’s Genesis mission, it appears that the Sun has a distinct oxygen isotopic composition from the terrestrial planets, asteroids, and comets. These differences cannot be explained by mass-dependent diffusion and require a physical-chemical mechanism or mechanisms that separate oxygen isotopes in a non-mass dependent manner.Several hypothesis have been proposed to explain the anomalous distribution. Photochemical self-shielding of CO may explain the anomalous distribution, however, this mechanism has key weaknesses including the requirement of a very fine tuned timescale to explain the isotopic differences between the Sun and bulk of the terrestrial planets. Recently, attention has been directed at understanding specific chemical reactions that occur on interstellar dust grains due to their similarities with non-equilibrium photochemical reactions believed to be responsible for the mass-independent isotopic fractionation patterns observed in Earth’s atmosphere. A specific focus has been directed towards understanding the formation of H2O because some of its precursor (HO2, and O3) are well-known to acquire mass-independent isotopic signatures when formed in the gas-phase.In this presentation, I describe a series of laboratory astrophysical experiments whose goal is to understand the distribution of oxygen isotopes in the solar system and perhaps, by extension, the distribution in other planetary systems. Preliminary results for the isotopic composition of O3 formed at 5K will be presented as well as the first, to our knowledge, measurements of the isotopic composition of H2O (18O/16O, 17O/16O, D/H) formed at 32K. We find that H2O formed in the astrophysical conditions we simulated acquired an anomalous isotopic composition with a triple

  11. Stable carbon isotope ratios as proxies for CO2 migration: An experimental approach with analogue fluids

    NASA Astrophysics Data System (ADS)

    Myrttinen, A.; Becker, V.; Mayer, B.; Barth, J. A.

    2012-12-01

    Stable carbon isotope ratios have proven to be highly sensitive tracers of CO2 migration in the subsurface, provided that the δ13C value of injected CO2 is distinct from that of baseline carbon in the reservoir and in shallow aquifers. This is of great importance for tracing the movement and the fate of injected CO2 in storage reservoirs where fluid and gas samples for chemical and isotope analyses can be obtained. One fundamental aspect that needs to be considered is carbon isotope fractionation between the various dissolved inorganic carbon (DIC) species and sub- or super-critical CO2. Such isotope fractionation may occur at various stages of CO2 migration including, the initial stages of injection during CO2 dissolution; during possible CO2 desiccation in pores; during CO2 migration within the reservoir or even during potential leakage into the near-surface environment. The magnitude and direction of carbon isotope fractionation (1000lnαDIC-CO2) between the DIC species and the injected CO2 depends highly on temperature and pH. At shallow depths, where temperatures are moderate and pH values are typically close to neutral, HCO3- is the dominant form of DIC. Carbon isotope fractionation between CO2 and DIC is therefore expected to reach ~ +10 ‰, resulting in a more positive δ13C value of DIC compared to that of the injected CO2. On the other hand, during injection, elevated temperatures and pH values of below 6 are usually observed. Here, H2CO3 is the dominant form of DIC and carbon isotope fractionation of close to -1 ‰ is expected. However, literature data on isotope fractionation values between H2CO3 and CO2 at temperatures above ˜ 60 °C are limited. In order to investigate the effects of pH and temperature on carbon isotope fractionation at various subsurface conditions, including elevated temperatures and pressures typical for CO2 reservoirs, laboratory experiments with analogue fluids were conducted within the framework of the CO2ISO-LABEL project

  12. Sediment residence times constrained by uranium-series isotopes: A critical appraisal of the comminution approach

    NASA Astrophysics Data System (ADS)

    Handley, Heather K.; Turner, Simon; Afonso, Juan C.; Dosseto, Anthony; Cohen, Tim

    2013-02-01

    Quantifying the rates of landscape evolution in response to climate change is inhibited by the difficulty of dating the formation of continental detrital sediments. We present uranium isotope data for Cooper Creek palaeochannel sediments from the Lake Eyre Basin in semi-arid South Australia in order to attempt to determine the formation ages and hence residence times of the sediments. To calculate the amount of recoil loss of 234U, a key input parameter used in the comminution approach, we use two suggested methods (weighted geometric and surface area measurement with an incorporated fractal correction) and typical assumed input parameter values found in the literature. The calculated recoil loss factors and comminution ages are highly dependent on the method of recoil loss factor determination used and the chosen assumptions. To appraise the ramifications of the assumptions inherent in the comminution age approach and determine individual and combined comminution age uncertainties associated to each variable, Monte Carlo simulations were conducted for a synthetic sediment sample. Using a reasonable associated uncertainty for each input factor and including variations in the source rock and measured (234U/238U) ratios, the total combined uncertainty on comminution age in our simulation (for both methods of recoil loss factor estimation) can amount to ±220-280 ka. The modelling shows that small changes in assumed input values translate into large effects on absolute comminution age. To improve the accuracy of the technique and provide meaningful absolute comminution ages, much tighter constraints are required on the assumptions for input factors such as the fraction of α-recoil lost 234Th and the initial (234U/238U) ratio of the source material. In order to be able to directly compare calculated comminution ages produced by different research groups, the standardisation of pre-treatment procedures, recoil loss factor estimation and assumed input parameter values

  13. Origins and processes of groundwater salinization in the urban coastal aquifers of Recife (Pernambuco, Brazil): A multi-isotope approach.

    PubMed

    Cary, Lise; Petelet-Giraud, Emmanuelle; Bertrand, Guillaume; Kloppmann, Wolfram; Aquilina, Luc; Martins, Veridiana; Hirata, Ricardo; Montenegro, Suzana; Pauwels, Hélène; Chatton, Eliot; Franzen, Melissa; Aurouet, Axel

    2015-10-15

    In the coastal multilayer aquifer system of a highly urbanized southern city (Recife, Brazil), where groundwaters are affected by salinization, a multi-isotope approach (Sr, B, O, H) was used to investigate the sources and processes of salinization. The high diversity of the geological bodies, built since the Atlantic opening during the Cretaceous, highly constrains the heterogeneity of the groundwater chemistry, e.g. Sr isotope ratios, and needs to be integrated to explain the salinization processes and groundwater pathways. A paleoseawater intrusion, most probably the 120 kyB.P. Pleistocene marine transgression, and cationic exchange are clearly evidenced in the most salinized parts of the Cabo and Beberibe aquifers. All (87)Sr/(86)Sr values are above the past and present-day seawater signatures, meaning that the Sr isotopic signature is altered due to additional Sr inputs from dilution with different freshwaters, and water-rock interactions. Only the Cabo aquifer presents a well-delimitated area of Na-HCO3 water typical of a freshening process. The two deep aquifers also display a broad range of B concentrations and B isotope ratios with values among the highest known to date (63-68.5‰). This suggests multiple sources and processes affecting B behavior, among which mixing with saline water, B sorption on clays and mixing with wastewater. The highly fractionated B isotopic values were explained by infiltration of relatively salty water with B interacting with clays, pointing out the major role played by (palaeo)-channels for the deep Beberibe aquifer recharge. Based on an increase of salinity at the end of the dry season, a present-day seawater intrusion is identified in the surficial Boa Viagem aquifer. Our conceptual model presents a comprehensive understanding of the major groundwater salinization pathways and processes, and should be of benefit for other southern Atlantic coastal aquifers to better address groundwater management issues. PMID:26063126

  14. A new approach for modeling Cenozoic oceanic lithium isotope paleo-variations: the key role of climate

    NASA Astrophysics Data System (ADS)

    Vigier, N.; Goddéris, Y.

    2015-04-01

    The marine record of ocean lithium isotope composition may provide important information constraining the factors that control continental weathering and how they have varied in the past. However, the equations establishing links between the continental flux of Li to the ocean, the continental Li isotope composition and the ocean Li isotope composition are under-constrained, and their resolution are related to significant uncertainties. In order to partially reduce this uncertainty, we propose a new approach that couples the C and Li cycles, such that our proposed reconstruction of the Cenozoic Li cycle is compatible with the required stability of the exospheric carbon cycle on geological timescales. The results of this exercise show, contrary to expectations, that the Cenozoic evolution of the Li isotope composition of rivers did not necessarily mimic the oceanic δ7Li rise. In contrast, variations in the continental flux of Li to the ocean are demonstrated to play a major role in setting the ocean δ7Li. We also provide evidence that Li storage in secondary phases is an important element of the global Li cycle that cannot be neglected, in particular during the early Cenozoic. Our modeling of the published foraminifera record highlights a close link between soil formation rate and indexes recording the climate evolution during the Cenozoic, such as foraminifera δ18O and pCO2 reconstructions. This leads us to conclude that the Li isotope record does not provide persuasive, unique evidence for erosional forcing of Cenozoic change because it could alternatively be consistent with a climatic control on soil production rates.

  15. High-resolution analysis of Quaternary calcretes: a coupled stable isotope and micromorphological approach

    NASA Astrophysics Data System (ADS)

    Adamson, Kathryn; Candy, Ian; Whitfield, Liz

    2015-04-01

    Pedogenic calcretes are abundant in arid and semi-arid regions, and they are widely used as proxy records of palaeoclimatic change. Calcrete oxygen (δ18O) and carbon (δ13C) isotopic signatures are indicative of temperature, aridity, or vegetation at the time of calcrete formation. Their microfabrics also reflect carbonate formation mechanisms in response to the prevailing environmental conditions. Many studies have explored calcrete micromorphology or stable isotope composition, but these techniques have not yet been applied simultaneously. This co-analysis is important as it allows us to establish whether calcrete morphology directly reflects environmental change. This study tests the potential of combining these analyses to examine the relationships between calcrete microfabrics, their isotopic signals, and Quaternary climate change. Calcretes from four river terraces of the Rio Alias in southeast Spain have been analysed in detail. On the basis of morphostratigraphic correlation (Maher et al., 2007) and Uranium-series ages (Candy et al., 2005), these span the period from 304 ± 26 ka (MIS 9) to the Holocene. The oldest profiles have therefore been exposed to multiple glacial-interglacial cycles. A total of 37 micromorphological profiles have been used to extract stable oxygen and carbon isotopic indicators from 77 microfacies. The morphological and isotopic complexity of the calcrete profiles increases with progressive age. The oldest samples display multiple calcretisation phases, and their microfabrics have a larger isotopic range than the younger samples. Alpha (non-biogenic) fabrics have higher δ13C and δ18O values than beta (biogenic) fabrics. Strong positive covariance between δ13C and δ18O within all profiles suggests that both isotopes are responding to the same environmental parameter. We suggest that this is relative aridity. The study demonstrates that the detailed co-analysis of calcrete micromorphology and stable isotope signatures allows

  16. Comparison of deterministic and stochastic approaches for isotopic concentration and decay heat uncertainty quantification on elementary fission pulse

    NASA Astrophysics Data System (ADS)

    Lahaye, S.; Huynh, T. D.; Tsilanizara, A.

    2016-03-01

    Uncertainty quantification of interest outputs in nuclear fuel cycle is an important issue for nuclear safety, from nuclear facilities to long term deposits. Most of those outputs are functions of the isotopic vector density which is estimated by fuel cycle codes, such as DARWIN/PEPIN2, MENDEL, ORIGEN or FISPACT. CEA code systems DARWIN/PEPIN2 and MENDEL propagate by two different methods the uncertainty from nuclear data inputs to isotopic concentrations and decay heat. This paper shows comparisons between those two codes on a Uranium-235 thermal fission pulse. Effects of nuclear data evaluation's choice (ENDF/B-VII.1, JEFF-3.1.1 and JENDL-2011) is inspected in this paper. All results show good agreement between both codes and methods, ensuring the reliability of both approaches for a given evaluation.

  17. Multiple taxon multiple locality approach to providing oxygen isotope evidence for warm-blooded theropod dinosaurs

    NASA Astrophysics Data System (ADS)

    Fricke, Henry C.; Rogers, Raymond R.

    2000-09-01

    Oxygen isotope ratios of fossil remains of coexisting taxa from several different localities can be used to help investigate dinosaur thermoregulation. Focusing on the Late Cretaceous, oxygen isotope ratios of crocodile tooth enamel from four separate localities exhibit less of a decrease with latitude than do ratios of tooth enamel from coexisting theropod dinosaurs. A shallower latitudinal gradient for crocodiles is consistent with how oxygen isotope ratios should vary for heterothermic animals having body temperatures coupled with their environments (“cold blooded”), while a steeper gradient for theropods is consistent with how these ratios should vary for homeothermic animals having constant body temperatures independent of their environments (“warm blooded”). This inferred homoethermy in theropods is likely due to higher rates of metabolic heat production relative to crocodiles and is not an artifact of body size.

  18. Dissolved Organic Carbon Cycling in Forested Watersheds: A Carbon Isotope Approach

    NASA Astrophysics Data System (ADS)

    Schiff, S. L.; Aravena, R.; Trumbore, S. E.; Dillon, P. J.

    1990-12-01

    Dissolved organic carbon (DOC) is important in the acid-base chemistry of acid-sensitive freshwater systems; in the complexation, mobility, persistence, and toxicity of metals and other pollutants; and in lake carbon metabolism. Carbon isotopes (13C and 14C) are used to study the origin, transport, and fate of DOC in a softwater catchment in central Ontario. Precipitation, soil percolates, groundwaters, stream, beaver pond, and lake waters, and lake sediment pore water were characterized chemically and isotopically. In addition to total DOC, isotopic measurements were made on the humic and fulvic DOC fractions. The lake is a net sink for DOC. Δ14C results indicate that the turnover time of most of the DOC in streams, lakes, and wetlands is fast, less than 40 years, and on the same time scale as changes in acidic deposition. DOC in groundwaters is composed of older carbon than surface waters, indicating extensive cycling of DOC in the upper soil zone or aquifer.

  19. Record of seasonal body fluid composition in Black Clam (Bivalve) using clumped isotope thermometric approach

    NASA Astrophysics Data System (ADS)

    Rahman, H.; Naidu, P. K.; Ghosh, P.

    2012-12-01

    Application of clumped isotope thermometry (Ghosh et al., 2006) is highly debated while resolving the issue of kinetic effect during biogenic carbonate precipitation. Mollusks are particularly attractive target to study the kinetic effect (Eiler, 2011) in the biological system owing to its incremental growth ring patterns. This allows understanding the role of environmental parameters other than temperature driving the distribution of heavier isotopologues. Guo et al., (2010) indicated role of pH in driving the distribution of heavier isotopolgues in the carbonates. We investigated here clumped isotopic composition of Black Calm (bivalve shell) caught live from a location in Southern Indian Estuary. The region experiences large change in seasonal condition. The physical environmental parameters at that location were monitored for last 3 years at monthly interval. The salinity, temperature, pH information are available for all the months when mollusc growth bands are deposited. The bottom water of estuary, where bivalve thrives experience maximum temperature of 32°C during November and December, while temperature during Monsoon months (July, August) drops lows to 26°C. Initial results on clumped isotope thermometry on the growth bands precipitated suggests that during the time in a year when pH level is alkaline i.e. 8.0±0.2 there is large consistency between actual temperature and estimated temperature using clumped isotope based thermometry. While the pH drops towards acidic i.e. 6.8±0.1 lower temperature estimates compared to actual was recorded. The effect of metabolic rate and body temperature variability is not been investigated as suggested in case of land snails based clumped isotope thermometry (Zaarur et al., 2011). Mollusc shell can be used to trace the composition of environmental water while pH variation is minimal. In this presentation analyses of more shell specimen and explore the role of pH and osmo-regulation in mollusc determining the clumped

  20. Proper interpretation of dissolved nitrous oxide isotopes, production pathways, and emissions requires a modelling approach.

    PubMed

    Thuss, Simon J; Venkiteswaran, Jason J; Schiff, Sherry L

    2014-01-01

    Stable isotopes ([Formula: see text]15N and [Formula: see text]18O) of the greenhouse gas N2O provide information about the sources and processes leading to N2O production and emission from aquatic ecosystems to the atmosphere. In turn, this describes the fate of nitrogen in the aquatic environment since N2O is an obligate intermediate of denitrification and can be a by-product of nitrification. However, due to exchange with the atmosphere, the [Formula: see text] values at typical concentrations in aquatic ecosystems differ significantly from both the source of N2O and the N2O emitted to the atmosphere. A dynamic model, SIDNO, was developed to explore the relationship between the isotopic ratios of N2O, N2O source, and the emitted N2O. If the N2O production rate or isotopic ratios vary, then the N2O concentration and isotopic ratios may vary or be constant, not necessarily concomitantly, depending on the synchronicity of production rate and source isotopic ratios. Thus prima facie interpretation of patterns in dissolved N2O concentrations and isotopic ratios is difficult. The dynamic model may be used to correctly interpret diel field data and allows for the estimation of the gas exchange coefficient, N2O production rate, and the production-weighted [Formula: see text] values of the N2O source in aquatic ecosystems. Combining field data with these modelling efforts allows this critical piece of nitrogen cycling and N2O flux to the atmosphere to be assessed. PMID:24608915

  1. Dual isotopic approach for determining groundwater origin and water-rock interactions in over exploited watershed in India

    NASA Astrophysics Data System (ADS)

    Negrel, Philippe; Pauwels, Hélène; Millot, Romain; Roy, Stéphane; Guerrot, Catherine

    2010-05-01

    isotopes in the return flow. In addition, such evaporation is further affected by land use, rice paddies having the strongest evapotranspiration. Lead concentrations span over one or two orders of magnitude up to approximately 20 ?g. L-1. Pb-isotopes, measured in water by MC-ICPMS using an improved new procedure, fluctuate largely as exemplified by the 206Pb/204Pb ratio, reaching values up to 25. Most of the lead in the groundwaters is of geogenic origin, and through the lead isotopic signature in groundwater we have traced and fingerprinted the processes of water-rock interactions considering the granite matrix. Combining a weathering model and field observations, we have defined a two step weathering process that includes a control on the Pb-isotopes ratios by accessory phases and by the main mineral from the granite in a second step of weathering. For future studies, multi-isotope approach will be necessary for the identification of possible flowpaths, in conjunction with the larger exploitation of the groundwater resources. This is also challenging for generalising the use of isotope tools (such as Nd, Sr, Pb and newly developed isotope systematics like Ca, Si...) in many other catchments that may face structural problems of groundwater overdraft.

  2. Selenium isotope geochemistry: A new approach to characterizing the environmental chemistry of selenium. Final report

    SciTech Connect

    Volpe, A.M.; Esser, B.K.

    1997-02-05

    High levels of selenium in the environment will be a prominent water quality issue in the western United States for many years. Selenium accumulation is linked to increased rates of death and deformity in migratory birds, blind staggers in livestock, and selenosis in humans. In California, agricultural drain waters and oil refinery effluent contribute to high selenium content in the San Joaquin Valley and the San Francisco Bay. The importance of these industries to California`s economy precludes simple abatement, while the complexity of selenium cycling precludes simple remediation. The purpose of this project is to measure variations in the isotopic composition of selenium in water and soil samples caused by natural processes and to show, for the first time, the value of isotopic measurements in characterizing selenium pollution. The research seeks to identify sources of selenium pollution, determine processes in the selenium cycle, and support selenium remediation studies. The project required the successful integration of three components: (1) appropriate sampling a field setting showing Se enrichment and possibly isotopic fractionation, (2) analytical chemical methods for isolating and purifying the various species of Se in waters and sediment, and (3) mass spectroscopic instrumentation for high precision isotope abundance measurements.

  3. MONITORING FOOD WEB CHANGES IN TIDE-RESTORED SALT MARSHES: A CARBON STABLE ISOTOPE APPROACH

    EPA Science Inventory

    Primary producer (angiosperms, macroalgae, submerged aquatic vegetation), suspended particulate matter, and Fundulus heteroclitus isotope values (d13C , d15N, d34S) were examined to assess their use as an indicator for changes in food web support functions in tidally-restored sal...

  4. Dynamical approach to isotopic-distribution of fission fragments from actinide nuclei

    NASA Astrophysics Data System (ADS)

    Ishizuka, Chikako; Chiba, Satoshi; Karpov, Alexander V.; Aritomo, Yoshihiro

    2016-06-01

    Measurements of the isotope distribution of fission fragments, often denoted as the primary fission yield (pre-neutron yield) or independent fission yield (post-neutron yield) are still challenging at low excitation energies, so that it is important to investigate it within a theory. Such quantities are vital for applications as well. In this study, fragment distributions from the fission of U isotopes at low excitation energies are studied using a dynamical model. The potential energy surface is derived from the two center shell model including the shell and pairing corrections. In order to calculate the charge distribution of fission fragments, we introduce a new parameter ηZ as the charge asymmetry, in addition to three parameters describing a nuclear shape, z as the distance between two centers of mass, δ as fragment deformation, and ηA as the mass asymmetry. Using this model, we calculated the isotopic distribution of 236U for the n-induced process 235U + n → 236U at low excitation energies. As a result, we found that the current model can well reproduce isotopic fission-fragment distribution which can be compared favorably with major libraries.

  5. Tracing the source of cooking oils with an integrated approach of using stable carbon isotope and fatty acid abundance.

    PubMed

    Liu, Weiguo; Yang, Hong; Wang, Zheng; Liu, Jinzhao

    2012-08-15

    We report a new approach to identify swill-cooked oils that are recycled from tainted food and livestock waste from commercial vegetable and animal oils by means of carbon isotope values and relative abundance of fatty acids. We test this method using 40 cooking oil samples of different types with known sources. We found significant differences in both total organic carbon isotope as well as compound-specific isotope values and fatty acid C(14)/C(18) ratios between commercial vegetable oils refined from C(3) plants (from -35.7 to -27.0‰ and from 0 to 0.15) and animal oils (from -28.3 to -14.3‰ and from 0.1 to 0.6). Tested swill-cooked oils, which were generally refined by mixing with animal waste illegally, fall into a narrow δ(13)C/fatty acid ratio distribution: from -25.9 to -24.1‰ and from 0.1 to 0.2. Our data demonstrate that the index of a cross-plotting between fatty acid δ(13)C values and C(14)/C(18) ratios can be used to distinguish clean commercial cooking oils from illegal swill-cooked oils. PMID:22813234

  6. A spatially explicit multi-isotope approach to map influence regions of plant-plant interactions after exotic plant invasion

    NASA Astrophysics Data System (ADS)

    Hellmann, Christine; Oldeland, Jens; Werner, Christiane

    2015-04-01

    Exotic plant invasions impose profound alterations to native ecosystems, including changes of water, carbon and nutrient cycles. However, explicitly quantifying these impacts remains a challenge. Stable isotopes, by providing natural tracers of biogeochemical processes, can help to identify and measure such alterations in space and time. Recently, δ15N isoscapes, i.e. spatially continuous representations of isotopic values, derived from native plant foliage, enabled to accurately trace nitrogen introduced by the N2-fixing invasive Acacia longifolia into a native Portuguese dune system. It could be shown that the area of the system which was altered by the invasive species exceeded the area which was covered by the invader by far. But still, definition of clear regions of influence is to some extent ambiguous. Here, we present an approach using multiple isoscapes derived from measured foliar δ13C and δ15N values of a native, non-fixing species, Corema album. By clustering isotopic information, we obtained an objective classification of the study area. Properties and spatial position of clusters could be interpreted to distinguish areas that were or were not influenced by A. longifolia. Spatial clusters at locations where A. longifolia was present had δ15N values that were enriched, i.e. close to the atmospheric signal of 0 o compared to the depleted values of the uninvaded system (ca. -11 o). Furthermore, C. album individuals in these clusters were characterized by higher foliar N content and enriched δ13C. These results indicate that the N2-fixing A. longifolia added nitrogen to the system which originated from the atmosphere and was used by the native C. album, inducing functional changes, i.e. an increase in WUE. Additionally, clusters were identified that were presumably determined by inherent properties of the native system. Thus, combining isotope ecology with geostatistical methods is a promising approach for mapping regions of influence in multi-isotope

  7. Sr Isotopes and human skeletal remains, improving a methodological approach in migration studies

    NASA Astrophysics Data System (ADS)

    Solis Pichardo, G.; Schaaf, P. E.; Hernandez, T.; Horn, P.; Manzanilla, L. R.

    2013-12-01

    Asserting mobility of ancient humans is a major issue for anthropologists. Sr isotopes are widely used in anthropological sciences to trace human migration histories from ancient burials. Sr in bone approximately reflects the isotopic composition of the geological region where the person lived before death; whereas the Sr isotopic system in tooth enamel is thought to remain as a closed system and thus conserves the isotope ratio acquired during childhood. A comparison of the 87Sr/86Sr ratios found in tooth enamel and in bone is performed to determine if the human skeletal remains belonged to a local or a migrant. Until now, tooth enamel was considered to be less sensitive to secondary Sr contamination due to its higher crystallinity and larger sizes of the biogenic apatites in comparison to that in bone and dentine. In the past, enamel as well as bone material was powdered, dissolved and analyzed by thermal ionization mass spectrometry (TIMS). In this contribution we show, however, that simple dissolution of enamel frequently yields erroneous results. Tooth enamel is often affected by secondary strontium contamination processes such as caries or diagenetic and environmental input, which can change the original isotopic composition. To avoid these problems we introduced a pre-treatment and three-step leaching procedure in enamel samples. Leaching is carried out with acetic acid of different concentrations, yielding two leachates and one residue of each sample. Frequently the 87Sr/86Sr results of the three leachates display different values confirming that secondary contamination did occur. Several examples from Teotihuacan, central Mexico demonstrate that enamel 87Sr/86Sr without leaching can show correct biogenic values, but there is also a considerable probability for these values to represent a mixture of original and secondary Sr without significance for migration reconstructions. Only the residue value is interpreted by us as the representative ratio for

  8. Dynamics of Zn in an urban wetland soil-plant system: Coupling isotopic and EXAFS approaches

    NASA Astrophysics Data System (ADS)

    Aucour, Anne-Marie; Bedell, Jean-Philippe; Queyron, Marine; Magnin, Valérie; Testemale, Denis; Sarret, Géraldine

    2015-07-01

    Plants play a key role in the stabilization of metals in contaminated environments. Studies have been performed on Zn uptake and storage mechanisms, mainly for Zn hyperaccumulating plants, though less is known about Zn stabilization in the rhizosphere of non-accumulating plants. This study was focused on the dynamics of Zn in a whole soil-litter-plant system and the processes controlling Zn mobilization and stabilization. The site studied was an infiltration basin receiving urban stormwater, in which Phalaris arundinacea (reed canary grass) developed spontaneously. A combination of chemical extractions (CaCl2, DTPA), EXAFS spectroscopy and Zn stable isotope measurements was applied for the water inlet, soil, plant organs and decaying biomass. Zn speciation changed from the water inlet to the soil. In the soil, Zn was present as Zn-layered double hydroxide (Zn-LDH), tetrahedral and octahedral sorbed Zn species. The formation of Zn-LDH participates in Zn stabilization. Tetrahedral Zn species, which were partly DTPA exchangeable, were enriched in heavy isotopes, whereas octahedral Zn (Zn-LDH and sorbed species) were enriched in light isotopes. Based on a linear model between δ66Zn and Zn speciation, δ66Zn for pure tetrahedral and octahedral end-members were estimated at ca. 0.33‰ and 0.04‰, respectively. In the plant, a mixture of octahedral Zn (attributed to aqueous Zn-organic acid complexes present in the symplasm), and tetrahedral Zn (attributed to apoplasmic Zn-cell wall complexes) was observed in all organs. Large enrichment in light isotopes from the soil to the plant Δ66Zn (of ca. -0.6‰) was observed. The stem was enriched in light isotopes versus roots and, to a lesser extent, versus leaves. The results suggest that Zn was taken up via a low-affinity transport system and that Zn was sequestrated in the stem symplasm after transit through leaves. Finally, intense Zn exchanges were observed between the decaying biomass and the soil, with the sorption of

  9. A Metal Stable Isotope Approach to Understanding Uranium Mobility Across Roll Front Redox Boundaries

    NASA Astrophysics Data System (ADS)

    Brown, S. T.; Basu, A.; Christensen, J. N.; DePaolo, D. J.; Heikoop, J. M.; Reimus, P. W.; Maher, K.; Weaver, K. L.

    2015-12-01

    Sedimentary roll-front uranium (U) ore deposits are the principal source of U for nuclear fuel in the USA and an important part of the current all-of-the-above energy strategy. Mining of roll-front U ore in the USA is primarily by in situ alkaline oxidative dissolution of U minerals. There are significant environmental benefits to in situ mining including no mine tailings or radioactive dust, however, the long-term immobilization of U in the aquifer after the completion of mining remains uncertain. We have utilized the metal stable isotopes U, Se and Mo in groundwater from roll-front mines in Texas and Wyoming to quantify the aquifer redox conditions and predict the onset of U reduction after post mining aquifer restoration. Supporting information from the geochemistry of groundwater and aquifer sediments are used to understand the transport of U prior to and after in situ mining. Groundwater was collected across 4 mining units at the Rosita mine in the Texas coastal plain and 2 mining units at the Smith Ranch mine in the Powder River Basin, Wyoming. In general, the sampled waters are moderately reducing and ore zone wells contain the highest aqueous U concentrations. The lowest U concentrations occur in monitoring wells downgradient of the ore zone. 238U/235U is lowest in downgradient wells and is correlated with aqueous U concentrations. Rayleigh distillation models of the 238U/235U are consistent with U isotope fractionation factors of 1.0004-1.001, similar to lab-based studies. Based on these results we conclude that redox reactions continue to affect U distribution in the ore zone and downgradient regions. We also measured aqueous selenium isotope (δ82Se) and molybdenum isotope (δ98Mo) compositions in the Rosita groundwater. Se(VI) primarily occurs in the upgradient wells and is absent in most ore zone and downgradient wells. Rayleigh distillation models suggest reduction of Se(VI) along the groundwater flow path and when superimposed on the U isotope data

  10. Does exercise stimulate protein breakdown in humans. Isotopic approaches to the problem

    SciTech Connect

    Wolfe, R.R.

    1987-10-01

    Protein metabolism in exercise has been investigated for 100 yr, yet it is still unclear if exercise induces an increased rate of protein breakdown. We have recently addressed this general question in a series of experiments in human subjects using stable isotopic tracers. In this paper, the results of those studies are reviewed. We have found that in light exercise the de-carboxylation of leucine is increased. However, urea production is not increased correspondingly, nor is the rate of incorporation into urea of nitrogen from either leucine or lysine. Further complicating the picture is the fact that lysine de-carboxylation is not markedly elevated in exercise. From these studies, we must conclude that isotopic techniques which have achieved general acceptance in other circumstances cannot reliably be used to answer the question of whether exercise stimulates protein breakdown in humans. However, these methods do provide results which enable a better understanding of the metabolism of the individual amino acids in exercise.

  11. Migration dynamics of clupeoids in the Schelde estuary: A stable isotope approach

    NASA Astrophysics Data System (ADS)

    Guelinckx, Jef; Maes, Joachim; De Brabandere, Loreto; Dehairs, Frank; Ollevier, Frans

    2006-02-01

    Large numbers of young of the year herring ( Clupea harengus L.) and sprat ( Sprattus sprattus (L.)) typically enter and remain within North Sea estuaries during the winter months. The main purpose of this study was to examine their migration dynamics between the North Sea and the Schelde estuary using C and N stable isotopes. Prior to this, stomach contents were used to verify the isotopic differences between the food sources at the sampling stations. From May 2000 to April 2001 fish were collected monthly in the upper and lower estuary. Muscle tissue and stomach contents were analyzed for δ13C and δ15N using an EA-IRMS. Based on the stomach contents, it was demonstrated that δ15N could not be used as a tracer for fish migration because the longitudinal estuarine δ15N gradient had reversed completely during autumn. The δ13C gradient, however, was found to be reliable for studying fish movement in the Schelde estuary. Seasonal movements of clupeoids in the Schelde estuary were analyzed by separating the temporal abundance patterns into migration groups based on their muscle isotopic composition. Immigration and emigration seem to occur continuously throughout the year. Most exchange occurred in November. During winter, immigration remained high but gradually decreased. Although the herring and sprat abundance further declined in the estuary during February and March, large seaward emigration was not fully demonstrated. As temporal overlap between immigration and emigration is concluded the results support the hypothesis that migration to estuarine nurseries is individually based.

  12. Synthesis of stable isotope-labeled epothilone D using a degradation-reconstruction approach.

    PubMed

    Burrell, Richard C; Turley, Wesley A; Bonacorsi, Samuel J

    2015-07-01

    The stabilization of microtubules using epothilones represents a novel mechanism of action to treat Alzheimer's disease. Epothilone D is one such microtubule-stabilizing drug that has been investigated by Bristol-Myers Squibb. An important step in the development process was the synthesis of a stable isotope-labeled analog for use in bioanalytical assays to accurately quantify the concentration of the drug in biological samples. A novel synthetic route to stable isotope-labeled epothilone D is described. The synthetic route was based on a strategy to degrade epothilone B and then use that key intermediate to reconstruct stable isotope-labeled epothilone D. Epothilone B was treated with potassium osmate and sodium periodate. The thiazole moiety in epothilone B was efficiently cleaved to give (1S,3S,7S,10R,11S,12S,16R)-3-acetyl-7,11-dihydroxy-8,8,10,12,16-pentamethyl-4,17-dioxabicyclo[14.1.0]heptadecane-5,9-dione. The epoxide in the macrocyclic ring of that intermediate was cleanly removed by treatment with tungsten hexachloride and n-butyllithium to give the corresponding olefin (4S,7R,8S,9S,16S,Z)-16-acetyl-4,8-dihydroxy-5,5,7,9,13-pentamethyloxacyclohexadec-13-ene-2,6-dione. Bis(triethylsilyl) protection produced (4S,7R,8S,9S,16S,Z)-16-acetyl-5,5,7,9,13-pentamethyl-4,8-bis(triethylsilyloxy)-oxacyclohexadec-13-ene-2,6-dione. This intermediate was coupled to a stable isotope-labeled thiazole using a Wittig reaction as the key step to provide (13)C5, (15)N-labeled epothilone D. In summary, the synthesis was completed in nine total steps, only six of which involved isotopically labeled reagents. A total of 168 mg of (13)C5, (15)N-labeled epothilone D was prepared in an 8% overall yield from (13)C2, (15)N-labeled thioacetamide and (13)C3-labeled ethyl bromopyruvate. PMID:26158758

  13. Potential of calcium isotopes to identify fractionations in vegetation: experimental approach

    NASA Astrophysics Data System (ADS)

    Cobert, F.; Schmitt, A.; Bourgade, P.; Stille, P.; Chabaux, F. J.; Badot, P.; Jaegler, T.

    2010-12-01

    This study aims to better understand the role of vegetation on the Ca cycle at the level of the critical zone of the Earth, in order to specify the mechanisms controlling the Ca absorption by plants at the rock/plant interface. To do this, we performed experiments using hydroponic plant cultures in a way that we could control the cooccuring geochemical and biological processes and determine the impact of the nutritive solution on the Ca cycle within plants. A dicotyledon and calcicole plant with rapid growth, the French bean (Phaseolus vulgaris L.), has been chosen to have access to one complete growth cycle. Several experiments have been conducted with two Ca concentrations, 5 (L) and 60 (H) ppm and two pH values (4 and 6) in the nutritive solution, for which the Ca concentration was maintained constant, so its Ca content is considered to be infinite. We determined Ca concentrations and isotopic ratios in the nutritive solution and in different organs (main roots, secondary roots, old and young stems, old and young leaves and fruits) at two different growth stages (10 days and 6 weeks). Our results show, in accord with previously published field studies, that the bean organs are all enriched in the light 40Ca isotope compared to the nutritive solution (e.g. Wigand et al., 2005; Page et al., 2008; Cenki-Tok et al., 2009; Holmden and Bélanger, 2010). We identify two fractionation levels. The first occurs during the uptake of the nutrient elements by the lateral roots. This implies that the main mechanisms of light isotope enrichments in the plant are due to electrochemical gradient transport processes taking place at this interface. The second fractionation can be observed within the plant itself and is due to the nature of the considered organ itself. Indeed structural reservoirs (primary roots, stem, reproductive organs) incorporate more the light 40Ca isotope compared to the transfer reservoirs (lateral roots, xylem sap, leaves). This could be linked to ion

  14. Further verification of the isotope dilution approach for estimating the degree of participation of (/sup 3/H)thymidine in DNA synthesis in studies of aquatic bacterial production

    SciTech Connect

    Bell, R.T.

    1986-11-01

    The optimal concentration of (/sup 3/H)thymidine (i.e., the maximal degree of participation in DNA synthesis) as determined by adding increasing amounts of labeled thymidine at the same specific activity was similar to the concentration of thymidine inhibiting the de novo pathway as determined by isotope dilution plots. These experiments provide further verification of the isotope dilution approach for determining the degree of participation of (/sup 3/H)thymidine in DNA synthesis.

  15. Improvement of water and light availability after thinning at a xeric site: which matters more? A dual isotope approach.

    PubMed

    Giuggiola, Arnaud; Ogée, Jérôme; Rigling, Andreas; Gessler, Arthur; Bugmann, Harald; Treydte, Kerstin

    2016-04-01

    Thinning fosters individual tree growth by increasing the availability of water, light and nutrients. At sites where water rather than light is limiting, thinning also enhances soil evaporation and might not be beneficial. Detailed knowledge of the short- to long-term physiological response underlying the growth responses to thinning is crucial for the management of forests already suffering from recurrent drought-induced dieback. We applied a dual isotope approach together with mechanistic isotope models to study the physiological processes underlying long-term growth enhancement of heavily thinned Pinus sylvestris in a xeric forest in Switzerland. This approach allowed us to identify and disentangle thinning-induced changes in stomatal conductance and assimilation rate. At our xeric study site, the increase in stomatal conductance far outweighed the increase in assimilation, implying that growth release in heavily thinned trees is primarily driven by enhanced water availability rather than increased light availability. We conclude that in forests with relatively isohydric species (drought avoiders) that are growing close to their physiological limits, thinning is recommended to maintain a less negative water balance and thus foster tree growth, and ultimately the survival of forest trees under drought. PMID:26639082

  16. Food sources of wintering piscivorous waterbirds in coastal waters: A triple stable isotope approach for the southeastern Baltic Sea

    NASA Astrophysics Data System (ADS)

    Morkūnė, Rasa; Lesutienė, Jūratė; Barisevičiūtė, Rūta; Morkūnas, Julius; Gasiūnaitė, Zita R.

    2016-03-01

    This study uses a triple isotope approach (δ13C, δ15N, and δ34S) to quantify the main food sources for wintering piscivorous waterbirds in the coastal zone of the southeastern Baltic Sea. Significant differences of δ15N and δ34S values among pelagic fishes, benthic fishes, and benthopelagic European smelt (Osmerus eperlanus) were detected, while δ13C was similar among these sources. Using different combinations of δ13C, δ15N, and δ34S values in mixing models, we found that common guillemot (Uria aalge) and red-throated diver (Gavia stellata) mostly foraged on pelagic prey (50-70% and 51-56%, respectively), whereas great crested grebe (Podiceps cristatus) consumed benthic prey (48-53%). European smelt comprised a substantial proportion of the diet of studied birds (19-36%). A stable isotope approach can be recommended as a non-lethal method to study avian diets in the coastal waters of the Baltic Sea.

  17. Water and light improvement after thinning at a xeric site: Which weights the most? A dual isotope approach

    NASA Astrophysics Data System (ADS)

    Giuggiola, Arnaud; Ogée, Jérôme; Gessler, Arthur; Rigling, Andreas; Bugmann, Harald; Treydte, Kerstin

    2015-04-01

    Reductions in stand density foster individual tree growth due to increases of resources such as water, light and nutrients. Detailed knowledge of the short- to long-term physiological response underlying the growth response to thinning is crucial for the management of forests already suffering from recurrent drought-induced dieback. We applied a dual isotope approach together with mechanistic isotope models such as MuSICA to study the physiological processes underlying growth enhancement in a long-term thinning experiment in a xeric Pinus sylvestris forest in Switzerland. This approach allowed for identifying and disentangling changes in stomatal conductance and assimilation rate. Our results indicate that an increase in stomatal conductance outweighs an increase in assimilation, meaning that the observed growth releases in heavy thinned trees at our xeric site are primarily driven by enhanced water availability rather than by the increase in light availability. We conclude that in areas with isohydric species (drought avoiders) that tend to grow close to their physiological limits, thinning is highly recommended to maintain a less negative water balance and thus foster tree growth, and ultimately the survival rate of individual trees and forests.

  18. Apportioning sources of organic matter in streambed sediments: an integrated molecular and compound-specific stable isotope approach.

    PubMed

    Cooper, Richard J; Pedentchouk, Nikolai; Hiscock, Kevin M; Disdle, Paul; Krueger, Tobias; Rawlins, Barry G

    2015-07-01

    clearly demonstrate the effectiveness of an integrated molecular and stable isotope analysis for quantitatively apportioning, with uncertainty, plant-specific organic matter contributions to streambed sediments via a Bayesian mixing model approach. PMID:25817221

  19. Assessing CO2 emissions from Canada's oil sands developments - an inversion approach combined with stable isotope data

    NASA Astrophysics Data System (ADS)

    Kim, M. G.; Lin, J. C.; Huang, L.; Edwards, T. W.; Jones, J. P.; Polavarapu, S.; Nassar, R.

    2012-12-01

    Reducing uncertainties in the projections of atmospheric CO2 concentration levels relies on increasing our scientific understanding of the exchange processes between atmosphere and land at regional scales, which is highly dependent on climate, ecosystem processes, and anthropogenic disturbances. In order for researchers to reduce the uncertainties, a combined framework that mutually addresses these independent variables to account for each process is invaluable. In this research, an example of top-down inversion modeling approach that is combined with stable isotope measurement data is presented. The potential for the proposed analysis framework is demonstrated using the Stochastic Time-Inverted Lagrangian Transport (STILT) model runs combined with high precision CO2 concentration data measured at a Canadian greenhouse gas monitoring site as well as multiple tracers: stable isotopes and combustion-related species. This framework yields a unique regional scale constraint that can be used to relate the measured changes of tracer concentrations to processes in their upwind source regions. The inversion approach both reproduces source areas in a spatially explicit way through sophisticated Lagrangian transport modeling and infers emission processes that leave imprints on atmospheric tracers. The understanding gained through the combined approach can also be used to verify reported emissions as part of regulatory regimes. The results indicate that changes in CO2 concentration is strongly influenced by regional sources, including significant fossil fuel emissions, and that the combined approach can be used to test reported emissions of the greenhouse gas from oil sands developments. Also, methods to further reduce uncertainties in the retrieved emissions by incorporating additional constraints including tracer-to-tracer correlations and satellite measurements are discussed briefly.

  20. Isotopic Approaches to Allying Productivity and Sulfur Metabolism in Three Symbiotic Hydrothermal Vent Molluscs

    NASA Astrophysics Data System (ADS)

    Beinart, R.; Gartman, A.; Sanders, J. G.; Luther, G. W.; Girguis, P. R.

    2012-12-01

    Symbioses between animals and chemosynthetic bacteria predominate at hydrothermal vents. In these associations, the endosymbiotic bacteria utilize chemical reductants for the energy to support autotrophy, providing primary nutrition for the host. Despite their ubiquity at vents worldwide, little is known about the rates of productivity of these symbioses under different physico-chemical regimes or how their metabolism effects the local geochemical environment. To address this matter, we used high-pressure flow through incubations and stable isotopic tracers to maintain three genera of symbiotic mollusc - the gastropods Alviniconcha and Ifremeria, and the mussel Bathymodiolus - at vent-like conditions. Via the incorporation of isotopically labeled compounds, we assessed their productivity when using different reduced sulfur species as reductants. Using cyclic voltammetry, mass spectrometry and discrete geochemical analyses, we concurrently measured their effect on sulfur flux from the vessels. We found that the symbionts of all three genera can support autotrophy with hydrogen sulfide and thiosulfate, though at different rates. Additionally, by examining the rate of isotopic incorporation into biomass, we revealed intra-generic variability in productivity among the individuals in our experimental assemblages that are likely related to differences in the geochemical regime along the length of reactor. These geochemical gradients are due to the activity of other individuals within the vessel, since those organisms closest to the influent of the vent-like water had the highest measured carbon incorporation. Finally, we measured the uptake and excretion of sulfur species, which illustrate the degree to which these symbioses might impact local sulfur chemistry in situ. These experiments show that A) access to particular sulfur species differentially affects the productivity of vent symbioses, suggesting that competition for these substrates, both within and between host

  1. Dual-Labeled Near-Infrared/99mTc Imaging Probes Using PAMAM-Coated Silica Nanoparticles for the Imaging of HER2-Expressing Cancer Cells

    PubMed Central

    Yamaguchi, Haruka; Tsuchimochi, Makoto; Hayama, Kazuhide; Kawase, Tomoyuki; Tsubokawa, Norio

    2016-01-01

    We sought to develop dual-modality imaging probes using functionalized silica nanoparticles to target human epidermal growth factor receptor 2 (HER2)-overexpressing breast cancer cells and achieve efficient target imaging of HER2-expressing tumors. Polyamidoamine-based functionalized silica nanoparticles (PCSNs) for multimodal imaging were synthesized with near-infrared (NIR) fluorescence (indocyanine green (ICG)) and technetium-99m (99mTc) radioactivity. Anti-HER2 antibodies were bound to the labeled PCSNs. These dual-imaging probes were tested to image HER2-overexpressing breast carcinoma cells. In vivo imaging was also examined in breast tumor xenograft models in mice. SK-BR3 (HER2 positive) cells were imaged with stronger NIR fluorescent signals than that in MDA-MB231 (HER2 negative) cells. The increased radioactivity of the SK-BR3 cells was also confirmed by phosphor imaging. NIR images showed strong fluorescent signals in the SK-BR3 tumor model compared to muscle tissues and the MDA-MB231 tumor model. Automatic well counting results showed increased radioactivity in the SK-BR3 xenograft tumors. We developed functionalized silica nanoparticles loaded with 99mTc and ICG for the targeting and imaging of HER2-expressing cells. The dual-imaging probes efficiently imaged HER2-overexpressing cells. Although further studies are needed to produce efficient isotope labeling, the results suggest that the multifunctional silica nanoparticles are a promising vehicle for imaging specific components of the cell membrane in a dual-modality manner. PMID:27399687

  2. Dual-Labeled Near-Infrared/(99m)Tc Imaging Probes Using PAMAM-Coated Silica Nanoparticles for the Imaging of HER2-Expressing Cancer Cells.

    PubMed

    Yamaguchi, Haruka; Tsuchimochi, Makoto; Hayama, Kazuhide; Kawase, Tomoyuki; Tsubokawa, Norio

    2016-01-01

    We sought to develop dual-modality imaging probes using functionalized silica nanoparticles to target human epidermal growth factor receptor 2 (HER2)-overexpressing breast cancer cells and achieve efficient target imaging of HER2-expressing tumors. Polyamidoamine-based functionalized silica nanoparticles (PCSNs) for multimodal imaging were synthesized with near-infrared (NIR) fluorescence (indocyanine green (ICG)) and technetium-99m ((99m)Tc) radioactivity. Anti-HER2 antibodies were bound to the labeled PCSNs. These dual-imaging probes were tested to image HER2-overexpressing breast carcinoma cells. In vivo imaging was also examined in breast tumor xenograft models in mice. SK-BR3 (HER2 positive) cells were imaged with stronger NIR fluorescent signals than that in MDA-MB231 (HER2 negative) cells. The increased radioactivity of the SK-BR3 cells was also confirmed by phosphor imaging. NIR images showed strong fluorescent signals in the SK-BR3 tumor model compared to muscle tissues and the MDA-MB231 tumor model. Automatic well counting results showed increased radioactivity in the SK-BR3 xenograft tumors. We developed functionalized silica nanoparticles loaded with (99m)Tc and ICG for the targeting and imaging of HER2-expressing cells. The dual-imaging probes efficiently imaged HER2-overexpressing cells. Although further studies are needed to produce efficient isotope labeling, the results suggest that the multifunctional silica nanoparticles are a promising vehicle for imaging specific components of the cell membrane in a dual-modality manner. PMID:27399687

  3. An air-tolerant approach to the carbonylative Suzuki-Miyaura coupling: applications in isotope labeling.

    PubMed

    Ahlburg, Andreas; Lindhardt, Anders T; Taaning, Rolf H; Modvig, Amalie E; Skrydstrup, Troels

    2013-10-18

    Carbonylative Suzuki-Miyaura coupling conditions have been developed that proceed without the exclusion of oxygen and in the presence of nondegassed and nondried solvents. By adapting the method to a two-chamber setup, the direct handling of carbon monoxide, produced from stable CO precursors, is avoided. The protocol afforded the desired benzophenones with excellent functional group tolerance and in good yields. Substituting the CO precursor, in the CO-producing chamber, with its carbon-13 labeled version generated the corresponding carbon-13 labeled benzophenones. Finally, the developed system was applied in the synthesis and isotope labeling of two pharmaceuticals, nordazepam and Tricor. PMID:24004340

  4. Isotopic Approach to Soil Carbonate Dynamics and Implications for Paleoclimatic Interpretations

    USGS Publications Warehouse

    Pendall, E.G.; Harden, J.W.; Trumbore, S.E.; Chadwick, O.A.

    1994-01-01

    The radiocarbon content and stable isotope composition of soil carbonate are best described by a dynamic system in which isotopic reequilibration occurs as a result of recurrent dissolution and reprecipitation. Depth of water penetration into the soil profile, as well as soil age, determines the degree of carbonate isotope reequilibration. We measured ??13C, ??18O and radiocarbon content of gravel rinds and fine (<2 mm) carbonate in soils of 3 .different ages (1000, 3800, and 6300 14 C yr B.P.) to assess the degree to which they record and preserve a climatic signal. In soils developing in deposits independently dated at 3800 and 6300 radiocarbon yr B.P., carbonate radiocarbon content above 40 cm depth suggests continual dissolution and reprecipitation, presumably due to frequent wetting events. Between 40 and 90 cm depth, fine carbonate is dissolved and precipitated as rinds that are not redissolved subsequently. Below 90 cm depth in these soils, radiocarbon content indicates that inherited, fine carbonate undergoes little dissolution and reprecipitation. In the 3800- and 6300-yr-old soils, ??13C in rind and fine carbonate follows a decreasing trend with depth, apparently in equilibrium with modern soil gas, as predicted by a diffusive model for soil CO2. ??18O also decreases with depth due to greater evaporative enrichment above 50 cm depth. In contrast, carbonate isotopes in a 1000-yr-old deposit do not reflect modern conditions even in surficial horizons; this soil has not undergone significant pedogenesis. There appears to be a lag of at least 1000 but less than 3800 yr before carbonate inherited with parent material is modified by ambient climatic conditions. Although small amounts of carbonate are inherited with the parent material, the rate of pedogenic carbonate accumulation indicates that Ca is derived primarily from eolian and rainfall sources. A model describing carbonate input and radiocarbon decay suggests that fine carbonate below 90 cm is mostly

  5. A Nd Isotopic Composition Modeling Approach of the Oceanic Thermohaline Circulation Change During LGM

    NASA Astrophysics Data System (ADS)

    Arsouze, T.; Dutay, J.; Lacan, F.; Jeandel, C.; Alkama, R.; Kageyama, M.; Piotrowski, A.

    2006-12-01

    The role of thermohaline circulation in climate change has been a matter of debate for a long time. Proxies of past ocean circulation such as δ13C or 231Pa/230Th suggest a relationship between North Atlantic Deep Water (NADW) strength and rapid climate change. Neodymium isotopic composition (Nd IC) is a quasi conservative geochemical tracer of water masses in the ocean interior and thus can be used as a proxy for NADW. Seawater Nd IC being recorded in marine sediments, this proxy is used to infer paleo-circulations on various time scales. Recent studies of Nd IC records, in the ferromanganese oxide components of a South Atlantic core, confirm the close relation between thermohaline circulation and North Atlantic climate changes through the last deglaciation (Piotrowski et al., 2004). Our purpose here is to model the Nd IC during the LGM and the Holocene with the Ocean Global Circulation Model NEMO, in the ORCA2 (2°) configuration. The explicit simulation of this proxy in the model allows to investigate and quantify the circulation change that corresponds to the Nd isotopic composition variation recorded in the sediments. We consider that the main source of Nd into the ocean is the interaction between water masses and continental margins (Boundary Exchange process; (Lacan and Jeandel, 2005). Boundary exchange is parameterized using a relaxing term (Arsouze et al., 2006). Simulated Nd IC distributions are evaluated by comparison with available records for the LGM and Holocene. References: Arsouze, T., Dutay, J.-C., Lacan, F. and Jeandel, C., 2006. Modeling the neodymium isotopic composition with a global ocean circulation model Chemical Geology, in press. Lacan, F. and Jeandel, C., 2005. Neodymium isotopes as a new tool for quantifying exchange fluxes at the continent - ocean interface. Earth and Planetary Science Letters, 232(3-4): 245-257. Piotrowski, A.M., Goldstein, S.L., Hemming, S.R. and Fairbanks, R.G., 2004. Intensification and variability of ocean

  6. Contribution of recycled moisture to precipitation in oases of arid central Asia: A stable isotope approach

    NASA Astrophysics Data System (ADS)

    Wang, Shengjie; Zhang, Mingjun; Che, Yanjun; Chen, Fenli; Qiang, Fang

    2016-04-01

    Terrestrial moisture contributed by surface evaporation and transpiration, also known as recycled moisture, plays an important role in hydrological processes especially across arid central Asia. The stable hydrogen and oxygen isotopes can be used for water budget analysis to calculate the contribution of recycled moisture to precipitation between two locations along the moisture flow. Based on a three-component isotopic mixing model, the moisture recycling in oasis stations of arid central Asia during summer months is assessed. At large oases of Urumqi, the proportional contribution of recycled moisture to local precipitation is approximately 16.2%, and the mean proportions of surface evaporation and transpiration are 5.9% ± 1.5% and 10.3% ± 2.2%, respectively. At small oases like Shihezi and Caijiahu the contribution of recycled moisture is less than 5%, and the proportion of surface evaporation is much less than that of transpiration. The vegetative cover in arid central Asia is generally sparse, but the evapotranspiration contribution to precipitation cannot be ignored at the widely distributed oases. The oasis effect shows great variability depending on locations and water availability for evapotranspiration.

  7. Pathways of CH3Hg and Hg Ingestion in Benthic Organisms: An Enriched Isotope Approach

    PubMed Central

    2015-01-01

    Mercury is a widespread contaminant in marine food webs, and identifying uptake pathways of mercury species, CH3Hg+ and Hg2+, into low trophic level organisms is important to understanding its entry into marine food webs. Enriched stable isotope tracers were used to study benthic vs. pelagic pathways of CH3Hg+ and Hg2+ uptake via food to the infaunal estuarine amphipod, Leptocheirus plumulosus. Algal cells differentially labeled with isotopically enriched CH3Hg+ or Hg2+ were added simultaneously to the sediment and water column of microcosms, and Hg species were monitored in amphipods and in sediment and water compartments. Methylation of Hg2+ occurred during the course of the experiment, enhancing the uptake of Hg2+ spikes. Trophic transfer of Hg from algae added to the water column was determined to be the major uptake route for amphipods, suggesting inputs of contaminated organic matter from the pelagic zone are important to mercury bioaccumulation even in organisms living in sediments. PMID:24678910

  8. Towards a quantitative approach to the utilization of magnetic effects as a means of isotopic enrichment

    SciTech Connect

    Turro, N.J.

    1992-05-01

    The photolysis of methyldesoxybenzoin in sodium dodecyl sulfate micellar solutions, produces benzaldehyde and styrene as disproportionation products of the triplet geminate radical pair. We have found that both the benzaldehyde and the recovered methyldeoxybenzoin are enriched in 13-C. These results provide the first direct evidence that both recombination and disproportionation are identically selective to the magnetic isotope effect, an important point anticipated by theory, but previously untested. An investigation of the photostereoisomerization of the diasteromers of 2,4-diphenylpentane-3-one in micellar solutions has allowed a quantitative analysis of the probabilities of recombination of the micellized primary geminate radical pair toward formation of different combination products. The results show that within the confidence provided by highly accurate data, the primary geminate radical pairs recombine to regenerate the precursor substrate structure or diastereomer with equal probability.

  9. Isotope tracer approaches for characterizing artificial recharge and demonstrating regulatory compliance

    SciTech Connect

    Davisson, M.L.; Hudson, G.B.; Moran, J.E.; Neimeyer, S.; Herndon, R., LLNL

    1998-05-01

    Potable reuse of groundwater from wastewater origins requires new methods to quantify proposed regulatory criteria such as subsurface residence times, dilution, and water quality transitions. Isotope tracers oxygen-18 ({sup 18}O), tritium ({sup 3}H), dissolved noble gases, and radiocarbon ({sup 14}C) have been used together in Orange County to age-date groundwater, quantify mixing, and characterize changes in total organic carbon (TOC). Simultaneous measurements of {sup 3}H and helium-3 ({sup 3}He) are used to determine groundwater ages between 1 and 40 years with uncertainties of plus/minus one year. These ages map preferred groundwater flowpaths and identify groundwater ages of less than or equal to 1 year. Wells recharged from the Anaheim Lake spreading basin were used to monitor arrival times and dilution of 6000 acre-ft of {sup 18}O-distinct Colorado River (COR) water introduced during a controlled recharge experiment. In addition, isotopically enriched Xe was introduced into the basin to quantify COR dilution of greater than 90%. The COR arrived at 7 wells between 30 and 200 days after recharge commenced. The COR was diluted up to 90% at distances and depths less than 1000 feet from the lake. Results suggest that dilution of 50% is obtained within 6 months from time or recharge. {sup 14}C measured in TOC of Anaheim Lake bottom water was 3 pmc higher than the DOC. The same water collected one month later in a nearby monitoring well, as confirmed by {sup 18}O, showed a 50% reduction in TOC concentration, and a 7 pmc decrease in {sup 14}C relative to the surface water. This result suggests that older carbon components increase in TOC after recharge.

  10. Tracing carbon flow through coral reef food webs using a compound-specific stable isotope approach.

    PubMed

    McMahon, Kelton W; Thorrold, Simon R; Houghton, Leah A; Berumen, Michael L

    2016-03-01

    Coral reefs support spectacularly productive and diverse communities in tropical and sub-tropical waters throughout the world's oceans. Debate continues, however, on the degree to which reef biomass is supported by new water column production, benthic primary production, and recycled detrital carbon (C). We coupled compound-specific stable C isotope ratio (δ(13)C) analyses with Bayesian mixing models to quantify C flow from primary producers to coral reef fishes across multiple feeding guilds and trophic positions in the Red Sea. Analyses of reef fishes with putative diets composed primarily of zooplankton (Amblyglyphidodon indicus), benthic macroalgae (Stegastes nigricans), reef-associated detritus (Ctenochaetus striatus), and coral tissue (Chaetodon trifascialis) confirmed that δ(13)C values of essential amino acids from all baseline C sources were both isotopically diagnostic and accurately recorded in consumer tissues. While all four source end-members contributed to the production of coral reef fishes in our study, a single-source end-member often dominated dietary C assimilation of a given species, even for highly mobile, generalist top predators. Microbially reworked detritus was an important secondary C source for most species. Seascape configuration played an important role in structuring resource utilization patterns. For instance, Lutjanus ehrenbergii showed a significant shift from a benthic macroalgal food web on shelf reefs (71 ± 13 % of dietary C) to a phytoplankton-based food web (72 ± 11 %) on oceanic reefs. Our work provides insights into the roles that diverse C sources play in the structure and function of coral reef ecosystems and illustrates a powerful fingerprinting method to develop and test nutritional frameworks for understanding resource utilization. PMID:26590916

  11. Contribution to chlorine cycle: a Cl stable isotope approach on Mantle-Ocean exchanges

    NASA Astrophysics Data System (ADS)

    Bonifacie, M.; Jendrzejewski, N.; Pineau, F.; Agrinier, P.

    2003-04-01

    The stable isotope composition of chlorine (37Cl/35Cl) can be used to trace its geochemical cycle and is a powerfull tool to constrain the origin of high chlorine contents found for some fresh MORB glasses. Despite the fact that chlorine is a volatile element of primary importance, its cycle and isotopic fractionation factors during exchange processes between Earth's reservoirs or phases are poorly known. Furthermore, the scarcity of data for solid samples (rocks or minerals) reflects the analytical difficulty to extract chlorine from silicate structure. The classical methods of pyrohydrolysis followed by isotope-ratio mass spectrometric measurements on CH_3Cl gas have been optimised. Our technique represents the most quantitative and precise method of chlorine extraction for δ37Cl determination on solids published to date. Mean extraction yields are 100 ± 3%, δ37Cl values on duplicate extractions show reproducibility better than 0.2 ppm and the blanks represent less than 5% of the sample size. To characterise chlorine behaviour during the oceanic crust alteration, we have analysed fresh MORB glasses (from SWIR and EPR), altered basalts from leg 504B site (EPR), serpentinized peridotites (from SWIR and MAR) and an altered gabbro from the Hess Deep site (EPR). All samples (n=9) are depleted in 37Cl (δ37Cl from -1.4 to 0 ppm) relative to seawater (δ37Cl =0 ppm); Cl concentrations are between 200 and 2200 ppm. Our results on fresh MORBs: δ37Cl = -1.4 ppm and -0.6 ppm are in the lower range already published (-3 to +11 ppm, e.g. Magenheim et al., 95; Stewart, 2000). However, our δ37Cl range of altered samples: δ37Cl = -1.3 to -0.2 ppm (basalts, serpentinised peridotites and gabbro) is outside the range observed by Magenheim et al., 95 (+0.4 to +7.5 ppm in amphibole-rich rocks and smectite veins) despite the fact that in both study amphibole-rich rocks from the same site (i.e. leg 504B) have been analysed. On this site, our δ37Cl results are very homogeneous

  12. Approaching the Final Frontier in Lateral Resolution for Isotopic and Chemical Analysis with CHILI

    NASA Astrophysics Data System (ADS)

    Davis, A. M.; Stephan, T.; Pellin, M.; Savina, M.; Yokochi, R.; Trappitsch, R.; Liu, N.; King, A.

    2011-12-01

    The small sizes of samples returned by recent (Stardust, Hayabusa) and future (OSIRIS-REx) sample return missions to comets and asteroids, as well as the small sizes of presolar grains in and interplanetary dust particles (IDPs) are driving improvements in lateral resolution and sensitivity beyond what is available with current state-of-the-art secondary ion mass spectrometry (SIMS) instruments. SIMS lateral resolution has reached ~50 nm and useful yields are at most a few percent. We are completing construction of CHILI (the CHicago Instrument for Laser Ionization), a resonant ionization mass spectrometry (RIMS) nanobeam instrument designed for isotopic and chemical analysis at the few-nm scale with a useful yield of ≥35% [1]. CHILI is equipped with a COBRA-FIB high resolution liquid metal ion gun (LMIG) and an e-CLIPSE Plus field emission electron gun from Orsay Physics, each of which can be focused to <4 nm. The electron gun will be used for secondary electron imaging, as the built-in optical microscope is diffraction-limited to ~0.5 μm. A piezoelectric stage capable of reproducible nm-scale motions and equipped with a sample holder that will accept a wide variety of sample mounts is operational. The flight tube for the time-of-flight mass spectrometer mounted vertically above the sample chamber; this assembly is mounted in the center of an H-shaped laser table equipped with active vibration cancellation devices. The table has been demonstrated to have a vertical vibrational amplitude of less than 0.2 nm. Resonant ionization will be done with six Ti:sapphire tunable solid state lasers pumped with three 40W Nd:YLF lasers, which will allow two to three elements to be analyzed simultaneously. Ion detection in existing RIMS instruments [2,3] is done with a microchannel plate with a single anode. Isotope ratio precision is limited by counting statistics, as no more than one ion of the most abundant isotope of an element can be counted for each pulse. CHILI will

  13. A dual isotope approach to isolate soil carbon pools of different turnover times

    NASA Astrophysics Data System (ADS)

    Torn, M. S.; Kleber, M.; Zavaleta, E. S.; Zhu, B.; Field, C. B.; Trumbore, S. E.

    2013-12-01

    Soils are globally significant sources and sinks of atmospheric CO2. Increasing the resolution of soil carbon turnover estimates is important for predicting the response of soil carbon cycling to environmental change. We show that soil carbon turnover times can be more finely resolved using a dual isotope label like the one provided by elevated CO2 experiments that use fossil CO2. We modeled each soil physical fraction as two pools with different turnover times using the atmospheric 14C bomb spike in combination with the label in 14C and 13C provided by an elevated CO2 experiment in a California annual grassland. In sandstone and serpentine soils, the light fraction carbon was 21-54% fast cycling with 2-9 yr turnover, and 36-79% slow cycling with turnover slower than 100 yr. This validates model treatment of the light fraction as active and intermediate cycling carbon. The dense, mineral-associated fraction also had a very dynamic component, consisting of ∼7% fast-cycling carbon and ∼93% very slow cycling carbon. Similarly, half the microbial biomass carbon in the sandstone soil was more than 5 yr old, and 40% of the carbon respired by microbes had been fixed more than 5 yr ago. Resolving each density fraction into two pools revealed that only a small component of total soil carbon is responsible for most CO2 efflux from these soils. In the sandstone soil, 11% of soil carbon contributes more than 90% of the annual CO2 efflux. The fact that soil physical fractions, designed to isolate organic material of roughly homogeneous physico-chemical state, contain material of dramatically different turnover times is consistent with recent observations of rapid isotope incorporation into seemingly stable fractions and with emerging evidence for hot spots or micro-site variation of decomposition within the soil matrix. Predictions of soil carbon storage using a turnover time estimated with the assumption of a single pool per density fraction would greatly overestimate

  14. Approaching the N=82 shell closure with mass measurements of Ag and Cd isotopes

    SciTech Connect

    Breitenfeldt, M.; Baruah, S.; Rosenbusch, M.; Schweikhard, L.; Borgmann, Ch.; Boehm, Ch.; George, S.; Audi, G.; Lunney, D.; Minaya-Ramirez, E.; Naimi, S.; Beck, D.; Dworschak, M.; Herfurth, F.; Savreux, R.; Yazidjian, C.; Blaum, K.; Cakirli, R. B.; Casten, R. F.; Delahaye, P.

    2010-03-15

    Mass measurements of neutron-rich Cd and Ag isotopes were performed with the Penning trap mass spectrometer ISOLTRAP. The masses of {sup 112,114-124}Ag and {sup 114,120,122-124,126,128}Cd, determined with relative uncertainties between 2x10{sup -8} and 2x10{sup -7}, resulted in significant corrections and improvements of the mass surface. In particular, the mass of {sup 124}Ag was previously unknown. In addition, other masses that had to be inferred from Q values of nuclear decays and reactions have now been measured directly. The analysis includes various mass differences, namely the two-neutron separation energies, the applicability of the Garvey-Kelson relations, double differences of masses deltaV{sub pn}, which give empirical proton-neutron interaction strengths, as well as a comparison with recent microscopic calculations. The deltaV{sub pn} results reveal that for even-even nuclides around {sup 132}Sn the trends are similar to those in the {sup 208}Pb region.

  15. Measurement of human lung absorption of metaproterenol given via an aerosol using a stable isotope approach

    SciTech Connect

    MacGregor, T.R.

    1985-01-01

    The extent and rate of lung absorption of metaproterenol given via a metered dose aerosol was studied in normal, asthmatic, and chronic bronchitic volunteers. Aerosols of metaproterenol-d/sub 0/ and metaproterenol-/sup 13/C/sub 3/, 650 mcg doses each, were utilized followed in 3 hours by a 980 mcg intravenous infusion of metaproterenol-d/sub 7/. Pharmacokinetics of all three stable isotope formulations were studied in a 24 hour period in conjunction with pharmacologic effect measurements. A gas chromatographic/mass spectrometric assay for metaproterenol capable of reliably measuring plasma concentrations as low as 50 pg/mL was developed. Extent of lung absorption of metaproterenol following aerosol administration averaged 3% in normal and asthmatic volunteers (N = 6 each) and 1.8% in chronic bronchitic volunteers (N = 5). The extent absorbed on the second dose was comparable to the extent from the first dose. The rates of lung absorption, calculated by the Loo-Riegelman method, were bi-phasic in all volunteers with an initial, rapid first order phase followed by a slower, zero order phase. A working hypothesis, based on the solid suspension properties of the aerosol, was presented.

  16. Tracing of water masses using a multi isotope approach in the southern Indian Ocean

    NASA Astrophysics Data System (ADS)

    Povinec, P. P.; Breier, R.; Coppola, L.; Groening, M.; Jeandel, C.; Jull, A. J. T.; Kieser, W. E.; Lee, S.-H.; Liong Wee Kwong, L.; Morgenstern, U.; Park, Y.-H.; Top, Z.

    2011-02-01

    Anthropogenic radionuclides (3 H, 14 C, and 129I) stemmed from nuclear weapons tests were found in 1999 to be very abundant in the surface of the southern Indian Ocean, comparable to those in the subtropical Northwest Pacific Ocean. The observed radionuclide variations with latitude/longitude in the southern Indian Ocean are not due to deposition patterns of global fallout, but due to transport of water masses from the western Pacific through the Indonesian seas, and different water fronts present in the Crozet Basin of the Indian Ocean. High radionuclide concentrations observed in the latitudinal belt of 20-40°S are associated with the Indian Ocean Subtropical Gyre which acts as a reservoir of radionuclides, maintaining their high concentrations on a time scale of several decades. 14 C data documents that the southern Indian Ocean is an important for sink of anthropogenic carbon. The isotopic tracers reveal the evidence of the most intense surface gradients and presence of several water masses in the southern Indian Ocean, which makes the region one of the most dynamic places of the World Ocean.

  17. Fate of terrestrial DOC within stream biofilm communities: a stable isotope approach (Invited)

    NASA Astrophysics Data System (ADS)

    Wiegner, T. N.; Kaplan, L.; Ziegler, S. E.; Findlay, R. H.

    2010-12-01

    Heterotrophic members of the biofilm community play a critical ecological role in lotic ecosystems. They take up, degrade, and mineralize organic carbon, often dominate community respiration, and are a critical link to higher trophic levels through the microbial loop. The goal of our study was to identify who within the stream biofilm community actively metabolizes stream dissolved organic carbon (DOC) and ultimately controls stream ecosystem metabolism. This goal was accomplished by labeling heterotrophic members of the stream biofilm community in dark biofilm reactors through trace-additions of 13C-labeled tree tissue leachate (13C-DOC) in stream water for one month. Biofilm reactors receiving no 13C-DOC additions served as controls. Metabolic response of the biofilm community to the 13C-DOC additions was quantified through measures of DOC bioavailability, oxygen uptake, and bacterial production and abundance. Bioreactor community composition was assessed using phospholipid fatty acid (PLFA) biomarkers, and the metabolically active members of the community were identified through 13C isotopic analysis of the PLFAs. 13C-DOC additions increased DOC concentrations in stream water by 6% (±9) and changed the δ13C-DOC signature from -28‰ (±2) to +1021‰ (±763). 13C-DOC additions increased the bioavailable DOC in the stream water from 28% (±2) to 39% (±6), oxygen consumption from 20% (±5) to 33% (±9), bacterial cell abundance by a factor of 1.3, and total microbial biomass by a factor of 1.6, but did not significantly affect bacterial production. Bacteria comprised ~80% of the microbial community in the control and 13C-labeled reactors; the remainder of the microbial community was heterotrophic microeukaryotes. δ13C of PLFAs in the 13C-labeled biofilm reactors ranged from +246‰ to +1090‰ and were more depleted in 13C than the original 13C-DOC used to label them, suggesting preferential uptake of specific molecules within the 13C-DOC pool and

  18. New Approaches to Assessing and Predicting the Hydrologic Impacts of Urban Disturbance Using Isotopes and Transit Time Analysis

    NASA Astrophysics Data System (ADS)

    Soulsby, C.; Geris, J.; Birkel, C.; Tetzlaff, D.

    2015-12-01

    Urbanization is an abrupt hydrological disturbance that affects large parts of the world. For ameliorative management, an understanding of how flow partitioning and storage dynamics are affected is crucial, yet this remains limited. This reflects the lack of integrated monitoring and modelling frameworks for characterizing these hydrological response dynamics to incremental urban development. Here we use a coupled flow-isotope model to assess the impacts of urbanisation (~20%) on stream water age distributions in an 8 km2 catchment. A conceptual runoff model was used with flux tracking to estimate the time-varying age of stream water at the outlet and both urban and non-urban sub-catchments over a 3 year period. Combined objective functions of both flow and isotope metric constrained model structures, improved calibration and aided model evaluation. Specifically, we explored (1) the age distribution of stream water draining urban and non-urban areas, (2) the integrated effect of these different land uses at larger catchment scales, and (3) how the modelling can predict the impacts on the stream water age of future urbanization proposals. The results showed that stream water draining the most urbanized tributary was youngest with a mean transit time (MTT) of < 6 months compared with ~18 months in the non-urban tributary. For the catchment outlet, the MTT was around 9 months. Here, the response of urban areas dominated smaller and moderate events, but rural contributions dominated during the wettest periods, giving a bi-modal distribution of water ages. Predictions for planned developments in the area indicated that just a 5% increase in urban area would give dramatic reductions in MTTs that can propagate to the larger catchment scale. This novel approach offers a framework for understanding the cumulative impacts of disturbances on streams. It can also contribute to the design of more sustainable urban water design in terms of targeted restriction of rapid water

  19. Impact of different nitrogen emission sources on tree physiology as assessed by a triple stable isotope approach

    NASA Astrophysics Data System (ADS)

    Guerrieri, M. R.; Siegwolf, R. T. W.; Saurer, M.; Jäggi, M.; Cherubini, P.; Ripullone, F.; Borghetti, M.

    The importance that nitrogen (N) deposition has in driving the carbon (C) sequestration of forests has recently been investigated using both experimental and modeling approaches. Whether increased N deposition has positive or negative effects on such ecosystems depends on the status of the N and the duration of the deposition. By combining δ13C, δ18O, δ15N and dendrochronological approaches, we analyzed the impact of two different sources of NO x emissions on two tree species, namely: a broadleaved species ( Quercus cerris) that was located close to an oil refinery in Southern Italy, and a coniferous species ( Picea abies) located close to a freeway in Switzerland. Variations in the ci/ ca ratio and the distinction between stomatal and photosynthetic responses to NO x emissions in trees were assessed using a conceptual model, which combines δ13C and δ18O. δ15N in leaves, needles and tree rings was found to be a bioindicator of N input from anthropogenic emissions, especially at the oil refinery site. We observed that N fertilization had a stimulatory effect on tree growth near the oil refinery, while the opposite effect was found for trees at the freeway site. Changes in the ci/ ca ratio were mostly related to variations in δ13C at the freeway site and, thus, were driven by photosynthesis. At the oil refinery site they were mainly related to stomatal conductance, as assessed using δ18O. This study demonstrates that a single method approach does not always provide a complete picture of which physiological traits are more affected by N emissions. The triple isotope approach combined with dendrochronological analyses proved to be a very promising tool for monitoring the ecophysiological responses of trees to long-term N deposition.

  20. Examining the linkages between forest water use, hydrology, and climate using dual-isotope approaches: insights and challenges in headwater catchments (Invited)

    NASA Astrophysics Data System (ADS)

    Barnard, H. R.; Brooks, J. R.; Pypker, T. G.; McDonnell, J. J.; Bond, B. J.; Williams, D. G.

    2010-12-01

    The amount of biologically available water is arguably the central driver in plant processes. While many studies have examined the hydrological components of biologically available water, the role that vegetation water use plays within the forested ecosystem water balance is poorly understood. Fundamental questions of forests' effect on the hydrologic cycle remain unanswered. Stable isotope observations play an important role in studies that explore the interface between plant physiological function and watershed flowpaths, flow sources, and residence times. We use multiple approaches, including stable isotopes to mechanistically assess the inter-relationships between vegetation water use, hydrology, and climate. We measured deuterium and 18O of xylem water and soil water to track changes in the depth of transpiration source water throughout the summers in a headwater catchment in western Oregon. Additionally, we measured transpiration, soil moisture, and foliar pre-dawn water potential. Forest transpiration and soil evaporation are often not separately measured, and yet respond to environmental drivers in fundamentally different ways. A promising approach for partitioning the evapotranspiration into its component fluxes involves measurement of the stable isotope composition (2H and 18O) of water vapor exchanged between vegetation and atmosphere. We present some preliminary data examining changes in ET partitioning in response to bark beetles outbreaks in the Rocky Mountains. Last, to examine the linkages between vegetation function and micro-climate, we applied a dual isotope (13C and 18O) approach to infer physiological response of trees to changing environmental conditions. We found that stable isotopes of oxygen were directly related to stomatal conductance and inversely related to relative humidity; however, the relationship with relative humidity was more apparent. The correlation of stable isotopes in tree rings with environmental variables can be

  1. Tracing organic matter sources in a tropical mangrove ecosystem (Pichavaram, India) - a stable isotopic approach

    NASA Astrophysics Data System (ADS)

    Mohan Sappal, Swati; Jennerjahn, Tim; Ramanathan, Alagappan

    2014-05-01

    Mangroves are among the most productive ecosystems on earth and thus highly efficient carbon sinks with most of the carbon stored in the sediments. These are the sites for accumulation and preservation of both autochthonous and allochthonous organic matter (OM) due to their strategic location at the interface between land and sea and prevailing reducing environment. Recent studies suggest that vegetated coastal habitats are more important quantitative carbon sinks than previously thought. However, for global carbon budgets it is important to know whether the carbon buried is freshly fixed from atmospheric CO2 or relocated, and possibly very old, carbon from another reservoir. Therefore, the identification of OM sources is a critical issue for constructing the carbon budget in mangrove ecosystems so as to differentiate between the recent autochthonous or relocated allochthonous carbon that gets accumulated in the sediments. In this context the Pichavaram mangrove complex (comprising of a core mangrove area and the Vellar and Coleroon rivers) in the South of India was sampled along the estuarine gradient and in its different environmental settings, as these influence the carbon dynamics through differences in tidal flushing and relative importance of allochthonous versus autochthonous inputs. A total of 11 sediment cores, 18 surface sediments, 18 suspended sediment samples, 13 true mangrove plant species, 2 mangrove associate plants, 4 marsh shrub samples and 4 algae samples were collected from the Pichavaram mangrove complex in January 2012 and January 2013. The samples were analysed for carbon (C), nitrogen (N), stable carbon (δ13Corg) and stable nitrogen (δ15N) isotope composition. Our results highlight the relative abundance of terrestrial and mangrove derived organic matter over the marine dominated organic matter in the mangrove sediments. The sites with dense mangrove vegetation showed higher sediment carbon content as compared to the sites with degraded

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

    NASA Astrophysics Data System (ADS)

    Grottoli, A. G.

    2004-12-01

    natural field conditions corals feed on zooplankton below this `nutrient threshold' and that increases in heterotrophy should result in decreases skeletal δ 13C values. Overall, changes in photosynthesis and heterotrophy have significant effects on coral skeletal δ 13C. In shallower corals, photosynthesis drives the bulk of the variation in δ 13C. In addition, boron isotope data indicate that pH levels do not vary with changes in photosynthesis or heterotrophy suggesting that metabolically driven δ 13C fractionation during skeletogenesis is not pH driven. Thus the skeletal δ 13C records from shallow corals in non-upwelling regions where zooplankton concentrations are relatively constant should represent a reliable proxy of light variability. Due to the complexity associated with nutrients and heterotrophy, δ 13C records from upwelling regions or deep corals are still difficult to resolve.

  3. A combined hydrochemical - isotopic approach for assessing the regional pollution of an alluvial aquifer in a urbanized environment

    NASA Astrophysics Data System (ADS)

    Gesels, Julie; Orban, Philippe; Popescu, Cristina; Knöller, Kay; Brouyère, Serge

    2014-05-01

    The alluvial aquifer of the Meuse River is contaminated at regional scale in the urbanized and industrialized area of Liège in Belgium with different types of contaminants, in particular inorganics such as sulfate, nitrate and ammonium. The sources of those contaminants are numerous: brownfields, urban waste water, subsurface acid mine drainage from former coal mines, atmospheric deposits related to pollutants emissions in the atmosphere... Sulfate, nitrate and ammonium are both typical pollutants of the aquifer and tracers of the possible pollution sources. According to the European legislation on water, groundwater resources should reach a good quality status before 2015. However, an exemption can be obtained if it may be unfeasible or unreasonably expensive to achieve good status. In this case, groundwater quality objectives and management plans can be adapted to these specific conditions. To obtain such an exemption for the Meuse alluvial aquifer, it is required to demonstrate that the poor qualitative status is caused by acid mine drainage, or by widespread historical atmospheric deposition from industries, and not by recent anthropogenic contamination from the urban and industrial context. In this context, a detailed hydrogeochemical characterization of groundwater has been performed, with the aim of determining the origin of the inorganic contaminations and the main processes contributing to poor groundwater quality. A large hydrochemical sampling campaign was performed, based on 71 selected representative sampling locations, to better characterize the different vectors (end-members) of contamination of the alluvial aquifer and their respective contribution to groundwater contamination in the area. Groundwater samples were collected and analyzed for major and minor compounds and metallic trace elements. The analyses also include stable isotopes in water, sulfate, nitrate, ammonium, boron and strontium. Different hydrogeochemical approaches are combined to

  4. Experimental investigations of water fluxes within the soil-vegetation-atmosphere system: Stable isotope mass-balance approach to partition evaporation and transpiration

    NASA Astrophysics Data System (ADS)

    Wenninger, Jochen; Beza, Desta Tadesse; Uhlenbrook, Stefan

    Irrigated agriculture is the largest user of freshwater worldwide and the scale of irrigated agriculture can be so large that it can have dramatic effects on the water cycle and even alter regional climates. Therefore, it is vital to improve the water use efficiency of irrigated lands in order to address the sustainable use of water resources, the growing need for agricultural products, and the health of ecosystems. Environmental isotopes have unique attributes that make them particularly suitable for tracing hydrological pathways and quantifying hydrological fluxes within the soil-vegetation-atmosphere system. The stable isotopic composition of soil water is mainly controlled by precipitation or irrigation inputs and evaporative losses. Because transpiration does not fractionate soil water isotopes, it is possible to estimate the relative proportions of evaporation and transpiration using isotopic mass balance calculations. In this study experimental investigations, combining classical hydrometric measurements, tracer hydrological methods and a soil water model were applied to laboratory lysimeters to study the transpiration processes of Teff ( Eragrostis tea (Zucc.) Trotter). Teff is an annual bunch cereal and an important aliment in Ethiopia and Eritrea and it is also gaining popularity in other countries. To determine the soil water contents, sensors using a capacitance/frequency domain technology were installed at different depths and soil water samples for the isotope analysis were taken using pore water samplers. Water contents in different depths and water fluxes, such as percolation and evaporation were modeled using the HYDRUS-1D software package. By using an isotope mass balance model the total evaporation and the fractions between soil evaporation and transpiration could be determined. The water losses which were estimated using the isotope mass-balance approach are in good agreement with the measured values using classical hydrometric measurements. The

  5. Isotopically controlled semiconductors

    SciTech Connect

    Haller, Eugene E.

    2001-12-21

    Semiconductor bulk crystals and multilayer structures with controlled isotopic composition have attracted much scientific and technical interest in the past few years. Isotopic composition affects a large number of physical properties, including phonon energies and lifetimes, bandgaps, the thermal conductivity and expansion coefficient and spin-related effects. Isotope superlattices are ideal media for self-diffusion studies. In combination with neutron transmutation doping, isotope control offers a novel approach to metal-insulator transition studies. Spintronics, quantum computing and nanoparticle science are emerging fields using isotope control.

  6. Assessing sources of nitrate contamination in the Shiraz urban aquifer (Iran) using the δ(15)N and δ(18)O dual-isotope approach.

    PubMed

    Amiri, Haleh; Zare, Mohammad; Widory, David

    2015-01-01

    Nitrate ([Formula: see text]) is one of the major threats to the quality of the drinking water taken from the Shiraz aquifer. This aquifer undergoes high anthropogenic pressures from multiple local urban (including uncontrolled sewage systems), agricultural and industrial activities, resulting in [Formula: see text] concentrations as high as 149 mg L(-1), well above the 50 mg L(-1) guideline defined by the World Health Organisation. We coupled here classical chemical and dual isotope (δ(15)N and δ(18)O of [Formula: see text]) approaches trying to characterize sources and potential processes controlling the budget of this pollutant. Chemical data indicate that nitrate in this aquifer is explained by distinct end-members: while mineral fertilizers isotopically show to have no impact, our isotope approach identifies natural soil nitrification and organic [Formula: see text] (manure and/or septic waste) as the two main contributors. Isotope data suggest that natural denitrification may occur within the aquifer, but this conclusion is not supported by the study of other chemical parameters. PMID:25941866

  7. Drought Impact on Water - Carbon Interaction in Soil: A Stable Isotopic Approach

    NASA Astrophysics Data System (ADS)

    Joseph, J.; Weiler, M.; Gessler, A.

    2014-12-01

    Extreme climatic conditions like drought introduce drastic changes in carbon and water dynamics in the plant - soil continuum, starting from carbon assimilation till carbon allocation in the soil, root water uptake till transpiration via leaves. Our objective was to study the drought impact on the dynamics of Carbon, and water cycles, as well as the interaction between them under extreme climatic conditions in the plant soil continuum. The first phase of the experiment involved 13CO2 pulse labeling of drought exposed and well-water beech microcosms, during which we monitored the 13C allocation to roots, and in the soil by measuring the CO2 concentration, ∂13C, and ∂18O of root derived CO2. We found that drought had a significant impact on, a) carbon assimilation, allocation, and translocation rate in the plant - soil system. The drought stressed plants not only assimilated fewer amounts of CO2, but also translocation of those assimilates belowground was extremely slow, and root respiration was low in comparison the well watered control plants. The second phase involved rewetting of the drought chambers (and the application of similar amounts of water to the controls) using D218O enriched water followed by an additional 13CO2 pulse labeling approach so as to study the effects of drought on the infiltration patterns of a precipitation event as well as the recovery of the carbon relations of previously drought stressed beech saplings.

  8. A triple stable isotope approach in tree rings for detecting the impact of nitrogen emissions on tree physiology

    NASA Astrophysics Data System (ADS)

    Guerrieri, M. R.; Siegwolf, R. T. W.; Saurer, M.; Jaeggi, M.; Cherubini, P.; Ripullone, F.; Borghetti, M.

    2009-04-01

    the freeway site (Picea abies) the ci/ca ratio was mainly altered by variations in A, as assessed by d13C. This study highlights that a single method approach does not always provide a complete picture of which physiological traits are more affected by N emissions. While, the triple isotope approach in tree rings can give a differentiated insight into the A-gs relationship, representing a promising tool to investigate the long-term effect of N emissions on trees.

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

    NASA Astrophysics Data System (ADS)

    Schollaen, Karina; Helle, Gerhard

    2013-04-01

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

  10. Isotopic Approaches to Evaluate the Fate of Injected CO2 in Two Geological Storage Projects in Mature Oilfields in Canada

    NASA Astrophysics Data System (ADS)

    Mayer, B.; Johnson, G.; Nightingale, M.; Maurice, S.; Raistrick, M.; Taylor, S.; Hutcheon, I.; Perkins, E.

    2008-12-01

    Monitoring and verification of CO2 storage is an essential component of geological storage projects. We present evidence from two enhanced oil recovery projects in Canada that geochemical and isotopic techniques can be successfully used to trace the fate of injected CO2. Geochemical and isotopic data for fluids and gases obtained from multiple wells at the International Energy Agency Greenhouse Gas Weyburn CO2 Monitoring and Storage Project (Saskatchewan, Canada) and from the Penn West Pembina Cardium CO2-Enhanced Oil Recovery Monitoring Pilot (Alberta, Canada) were collected before and throughout the CO2 injection phase. Carbon isotope ratios of injected CO2 in the Weyburn project were significantly lower than those of background CO2 in the reservoir. In contrast, carbon isotope ratios of injected CO2 at Penn West's Pembina Cardium CO2-Enhanced Oil Recovery Monitoring Pilot were markedly higher than those of background CO2. After commencement of CO2 injection, the concentrations and carbon isotope values of CO2 and HCO3- in fluids and gases repeatedly obtained from monitoring wells were determined. Increasing CO2 and HCO3- concentrations in concert with carbon isotope values trending towards those of the injected CO2 revealed effective solubility and ionic trapping of injected CO2 at several monitoring wells at both study sites. In addition, changes in the oxygen isotope values of reservoir fluids provided independent evidence for dissolution of injected CO2 in the produced waters. We conclude that geochemical and isotopic monitoring techniques can play an essential role in verification of CO2 storage provided that the isotopic composition of the injected CO2 is distinct.

  11. Identifying source and formation altitudes of nitrates in drinking water from Réunion Island, France, using a multi-isotopic approach

    NASA Astrophysics Data System (ADS)

    Rogers, Karyne M.; Nicolini, Eric; Gauthier, Virginie

    2012-09-01

    Nitrate concentrations, water isotopes (δ2H and δ18Owater) and associated nitrate isotopes (δ15Nnitrate and δ18Onitrate) from 10 drinking water wells, 5 fresh water springs and the discharge from 3 wastewater treatment stations in Réunion Island, located in the Indian Ocean, were analysed. We used a multi isotopic approach to investigate the extent of nitrate contamination, nitrate formation altitude and source of nitrates in Réunion Island's principal aquifer. Water from these study sites contained between 0.1 and 85.3 mg/L nitrate. δ15Nnitrate values between + 6 and + 14‰ suggested the main sources of contamination were animal and/or human waste, rather than inorganic (synthetic) fertilisers, infiltrating through the subsurface into the saturated zone, due to rainfall leaching of the unsaturated zone at various altitudes of precipitation. Based on δ15Nnitrate values alone, it was not possible to distinguish between animal and human activities responsible for the contamination of each specific catchment. However, using a multi isotope approach (δ18Owater and δ15Nnitrate), it was possible to relate the average altitude of rainfall infiltration (δ18Owater) associated with the nitrate contamination (δ18Onitrate). This relationship between land use, rainfall recharge altitude and isotopic composition (δ15Nnitrate and δ18Owater) discriminated between the influences of human waste at lower (below 600 m elevation) or animal derived contamination (at elevations between 600 and 1300 m). By further comparing the theoretical altitude of nitrate formation calculated by the δ18Onitrate, it was possible to determine that only 5 out of 15 fresh water wells and springs followed the conservative nitrate formation mechanism of 2/3δ18Owater + 1/3δ18Oair, to give nitrate formation altitudes which corresponded to land use activities.

  12. Direct and indirect indicators to identify potential leakage of contaminants associated with unconventional oil and gas development based on conceptual geochemical and isotopic monitoring approaches

    NASA Astrophysics Data System (ADS)

    Humez, P.; Mayer, B.; Negrel, P. J.; Lions, J.; Lagneau, V.; Kloppmann, W.; Ing, J.; Becker, V.; Nightingale, M.

    2014-12-01

    The extraction of tightly bound natural gas and oil raises environmental concerns regarding shallow drinking water resources. These concerns include impacts of migration of contaminants through induced and natural fractures, drilling imperfections, wastewater discharge and accidental spills. Improved understanding of the fate and transport of contaminants through long-term monitoring, and sharing of data between industry, regulators and researchers will help to effectively manage risks for shallow water resources associated with the unconventional gas and oil industry. Based on the North-American experiences related to unconventional oil and gas resources and monitoring approaches developed in the Carbon Capture and Storage (CCS) context, we suggest conceptual models for monitoring the potential contamination of shallow aquifers overlying production zones. The strength of sensitive geochemical tracers is demonstrated based on conceptual approaches (e.g. diffusion model) and field and tracer studies (e.g. geochemical and isotopic monitoring) with three objectives: 1) characterize subsurface derived contaminants as direct geochemical and isotopic indicators; 2) assess geochemical processes enhanced by the fluid intrusion; 3) understand parameters and processes which could impact or alter the geochemical and isotopic signatures of the contaminants (e.g. microbial oxidation, migration or transport processes etc.) to determine indirect indicators of potential contaminant leakage. This comprehensive geochemical and isotope approach using direct and indirect indicators with the analyses of major and minor ions, trace elements, and δ11B, δ7Li, δ34SSO4, δ18OSO4, 87Sr/86Sr, δ18OH2O, and δ2HH2O values in the CO2FIELDLAB project (Humez et al., 2014) allowed discriminating reactive mechanisms from non-reactive mixing processes associated with gas leakage within a shallow aquifer. These and other results indicate that this conceptual approach is promising for monitoring

  13. Joint Application of Concentrations and Isotopic Signatures to Investigate the Global Atmospheric Carbon Monoxide Budget: Inverse Modeling Approach

    NASA Astrophysics Data System (ADS)

    Park, K.; Mak, J. E.; Emmons, L. K.

    2008-12-01

    Carbon monoxide is not only an important component for determining the atmospheric oxidizing capacity but also a key trace gas in the atmospheric chemistry of the Earth's background environment. The global CO cycle and its change are closely related to both the change of CO mixing ratio and the change of source strength. Previously, to estimate the global CO budget, most top-down estimation techniques have been applied the concentrations of CO solely. Since CO from certain sources has a unique isotopic signature, its isotopes provide additional information to constrain its sources. Thus, coupling the concentration and isotope fraction information enables to tightly constrain CO flux by its sources and allows better estimations on the global CO budget. MOZART4 (Model for Ozone And Related chemical Tracers), a 3-D global chemical transport model developed at NCAR, MPI for meteorology and NOAA/GFDL and is used to simulate the global CO concentration and its isotopic signature. Also, a tracer version of MOZART4 which tagged for C16O and C18O from each region and each source was developed to see their contributions to the atmosphere efficiently. Based on the nine-year-simulation results we analyze the influences of each source of CO to the isotopic signature and the concentration. Especially, the evaluations are focused on the oxygen isotope of CO (δ18O), which has not been extensively studied yet. To validate the model performance, CO concentrations and isotopic signatures measured from MPI, NIWA and our lab are compared to the modeled results. The MOZART4 reproduced observational data fairly well; especially in mid to high latitude northern hemisphere. Bayesian inversion techniques have been used to estimate the global CO budget with combining observed and modeled CO concentration. However, previous studies show significant differences in their estimations on CO source strengths. Because, in addition to the CO mixing ratio, isotopic signatures are independent tracers

  14. Identification of the nitrate contamination sources of the Brusselian sands groundwater body (Belgium) using a dual-isotope approach.

    PubMed

    Mattern, Samuel; Sebilo, Mathieu; Vanclooster, Marnik

    2011-09-01

    Isotopic fingerprinting is an advanced technique allowing the classification of the nitrate source pollution of groundwater, but needs further development and validation. In this study, we performed measurements of natural stable isotopic composition of nitrate ((15)N and (18)O) in the groundwater body of the Brussels sands (Belgium) and studied the spatial and temporal dynamics of the isotope signature of this aquifer. Potential nitrogen sources sampled in the region had isotopic signatures that fell within the corresponding typical ranges found in the literature. For a few monitoring stations, the isotopic data strongly suggest that the sources of nitrate are from mineral fertiliser origin, as used in agriculture and golf courses. Other stations suggest that manure leaching from unprotected stockpiles in farms, domestic gardening practices, septic tanks and probably cemeteries contribute to the nitrate pollution of this groundwater body. For most monitoring stations, nitrate originates from a mixing of several nitrogen sources. The isotopic signature of the groundwater body was poorly structured in space, but exhibited a clear temporal structure. This temporal structure could be explained by groundwater recharge dynamics and cycling process of nitrogen in the soil-nitrogen pool. PMID:21892890

  15. A retro-biosynthetic approach to the prediction of biosynthetic pathways from position-specific isotope analysis as shown for tramadol

    PubMed Central

    Romek, Katarzyna M.; Nun, Pierrick; Remaud, Gérald S.; Silvestre, Virginie; Taïwe, Germain Sotoing; Lecerf-Schmidt, Florine; Boumendjel, Ahcène; De Waard, Michel; Robins, Richard J.

    2015-01-01

    Tramadol, previously only known as a synthetic analgesic, has now been found in the bark and wood of roots of the African medicinal tree Nauclea latifolia. At present, no direct evidence is available as to the biosynthetic pathway of its unusual skeleton. To provide guidance as to possible biosynthetic precursors, we have adopted a novel approach of retro-biosynthesis based on the position-specific distribution of isotopes in the extracted compound. Relatively recent developments in isotope ratio monitoring by 13C NMR spectrometry make possible the measurement of the nonstatistical position-specific natural abundance distribution of 13C (δ13Ci) within the molecule with better than 1‰ precision. Very substantial variation in the 13C positional distribution is found: between δ13Ci = −11 and −53‰. Distribution is not random and it is argued that the pattern observed can substantially be interpreted in relation to known causes of isotope fractionation in natural products. Thus, a plausible biosynthetic scheme based on sound biosynthetic principals of precursor–substrate relationships can be proposed. In addition, data obtained from the 18O/16O ratios in the oxygen atoms of the compound add support to the deductions made from the carbon isotope analysis. This paper shows how the use of 13C NMR at natural abundance can help with proposing a biosynthetic route to compounds newly found in nature or those difficult to tackle by conventional means. PMID:26106160

  16. Detecting isotopic ratio outliers

    SciTech Connect

    Bayne, C.K.; Smith, D.H.

    1985-01-01

    An alternative method is proposed for improving isotopic ratio estimates. This method mathematically models pulse-count data and uses iterative reweighted Poisson regression to estimate model parameters to calculate the isotopic ratios. This computer-oriented approach provides theoretically better methods than conventional techniques to establish error limits and to identify outliers. 6 refs., 3 figs., 3 tabs.

  17. Multiple isotope (H, O, N, S and Sr) approach elucidates complex pollution causes in the shallow groundwaters of the Taipei urban area

    NASA Astrophysics Data System (ADS)

    Hosono, Takahiro; Wang, Chung-Ho; Umezawa, Yu; Nakano, Takanori; Onodera, Shin-ichi; Nagata, Toshi; Yoshimizu, Chikage; Tayasu, Ichiro; Taniguchi, Makoto

    2011-01-01

    SummaryDeterioration of the quality of groundwater under urban areas has become a major environmental concern worldwide. This paper presents a pilot case study (in the Taipei urban area) using multiple stable isotopes ( δDO and δ18OO, δ15N and δ18O, δ34S and δ18O, and 87Sr/ 86Sr) with the aim of understanding the subsurface nature and environmental status of such areas. A previous study has already characterized Taipei shallow groundwaters as sulfate-rich in comparison to other Southeast Asian metropolitan cities. Our chemical measurements clarified that the arsenic is the important environmental concerns in the aquifers. Dual isotope approaches for nitrate and sulfate suggested these ions were sourced mainly from municipal sewage leaking from sewer pipes in urbanized area, while chemical fertilizers applied in the local agricultural fields partly contribute in the suburb area. Significant decreases in nitrate and sulfate concentrations due to denitrification and sulfate reduction were observed in some groundwaters, which induced increases in isotope ratios up to 24.9‰ for δ15N and 27.2‰ for δ34S. Nitrate groundwater pollution in the Taipei Basin is not a subject of serious concern (<44 mg/L limit for NO3- for all analyzed samples) at the present time due to attenuation by denitrification. However, arsenic is preferentially released in groundwater (>100 μg/L) in anoxic environment under which sulfate reduction occurs. The Sr isotope data suggested that the arsenic is derived from alluvial deposits of Oligocene-Miocene sedimentary rock origin. This study disclosed the complex causes of environmental changes in Taipei urban shallow groundwater. It is also important as an excellent case study demonstrating the efficient use of multiple isotope diagnosis in the urban groundwater environmental field.

  18. Identification and characterisation of potential sources of nitrate pollution in the Marano Lagoon (Italy) applying a multi-isotope approach

    NASA Astrophysics Data System (ADS)

    Saccon, P.; Leis, A.; Marca, A.; Kaiser, J.; Campisi, L.; Böttcher, M. E.; Savarino, J.; Escher, P.; Eisenhauer, A.; Erbland, J.

    2012-04-01

    The isotopic composition of nitrate (δ15N, δ18O and Δ17O), boron (δ11B) and water (δ2H and δ18O) were used to identify and characterize of multiple nitrate pollution sources in the Marano Lagoon (Italy) and part of its catchment area. The stable isotopes in nitrate measured by the denitrifier method have been adopted to differentiate among nitrate coming from agriculture (synthetic and natural fertilizers), airborne nitrate and nitrate from nitrification processes in soils. Boron isotopes have been used to identify the impact of domestic wastewaters to the aquatic system using the LA-MC-ICP-MS method. The combined use of NO3 and B isotopes has proved to be an effective means in identifying multiple nitrate pollution sources because these isotopes co-migrate in many environmental settings, their isotopes are fractionated by different environmental processes, and because wastewater and fertilizers may have distinct isotopic signatures for N and B. The stable isotopes of water have been used to calculate mixing ratios between sea and fresh water as well as to estimate the mean altitude of the recharge area of surface waters. Additionally, the stable isotopes of sulphate (δ34S and δ18O) have been adopted to trace natural and anthropogenic sources of sulphur in agricultural watersheds as well as in coastal systems. In order to characterize the chemical composition of the different water types the concentration of Ca2+, Mg2+, Na+, K+, NH4+, NO3-, NO2-, Cl-, Br-, SO42-, HCO3-, PO43-, total phosphorus and total boron have been analyzed. Moreover, the physicochemical parameters such as pH, electrical conductivity, dissolved oxygen, salinity and temperature have been measured. To identify the origins and fate of nitrate a water monitoring program was implemented in the Marano lagoon and part of its catchment area. The water monitoring program involved the collection of water samples from the lagoon, its tributary rivers, the groundwater up-welling line, groundwater

  19. Possible food sources of macrozoobenthos in the manko mangrove ecosystem, okinawa (Japan): a stable isotope analysis approach.

    PubMed

    Wardiatno, Yusli; Mardiansyah; Prartono, Tri; Tsuchiya, Makoto

    2015-04-01

    Identifying potential food sources in mangrove ecosystems is complex because of the multifarious inputs from both land and sea. This study, which was conducted in the Manko mangrove ecosystem of Okinawa, Japan, determined the composition of the stable isotopes δ(13)C and δ(15)N in primary producers and macrozoobenthos to estimate the potential food sources assimilated and to elucidate the target trophic levels of the macrozoobenthos. We measured the two stable isotope signatures of three gastropods (Cerithidea sp., Cassidula mustelina, Peronia verruculata), two crabs (Grapsidae sp., Uca sp.), mangrove tree (Kandelia candel) leaves, and sediment from the mangrove ecosystem. The respective carbon and nitrogen isotope signature results were as follows: -22.4‰ and 8.6‰ for Cerithidea sp., -25.06‰ and 8‰ for C. mustelina, -22.58‰ and 8‰ for P. verruculata, -24.3‰ and 10.6‰ for unidentified Grapsidae, -21.87 ‰ and 11.5 ‰ for Uca sp., -29.81‰ and 11‰ for K. candel, and -24.23‰ and 7.2‰ for the sediment. The stable isotope assimilation signatures of the macrozoobenthos indicated sediment as their food source. Considering the trophic levels, the stable isotope values may also indicate that the five macrozoobenthos species were secondary or higher consumers. PMID:26019747

  20. Possible Food Sources of Macrozoobenthos in the Manko Mangrove Ecosystem, Okinawa (Japan): A Stable Isotope Analysis Approach

    PubMed Central

    Wardiatno, Yusli; Mardiansyah; Prartono, Tri; Tsuchiya, Makoto

    2015-01-01

    Identifying potential food sources in mangrove ecosystems is complex because of the multifarious inputs from both land and sea. This study, which was conducted in the Manko mangrove ecosystem of Okinawa, Japan, determined the composition of the stable isotopes δ13C and δ15N in primary producers and macrozoobenthos to estimate the potential food sources assimilated and to elucidate the target trophic levels of the macrozoobenthos. We measured the two stable isotope signatures of three gastropods (Cerithidea sp., Cassidula mustelina, Peronia verruculata), two crabs (Grapsidae sp., Uca sp.), mangrove tree (Kandelia candel) leaves, and sediment from the mangrove ecosystem. The respective carbon and nitrogen isotope signature results were as follows: −22.4‰ and 8.6‰ for Cerithidea sp., −25.06‰ and 8‰ for C. mustelina, −22.58‰ and 8‰ for P. verruculata, −24.3‰ and 10.6‰ for unidentified Grapsidae, −21.87 ‰ and 11.5 ‰ for Uca sp., −29.81‰ and 11‰ for K. candel, and −24.23‰ and 7.2‰ for the sediment. The stable isotope assimilation signatures of the macrozoobenthos indicated sediment as their food source. Considering the trophic levels, the stable isotope values may also indicate that the five macrozoobenthos species were secondary or higher consumers. PMID:26019747

  1. Identifying nitrogen sources to thermal tide pools in Kapoho, Hawai'i, U.S.A, using a multi-stable isotope approach.

    PubMed

    Wiegner, Tracy N; Mokiao-Lee, Ambyr U; Johnson, Erik E

    2016-02-15

    Nitrogen (N) enrichment often results in coastal eutrophication, even in remote areas like Hawai'i. Therefore, determining N sources to coastal waters is important for their management. This study identified N sources to tide pools in Kapoho, Hawai'i, and determined their relative importance using three stable isotopes (δ(15)N, δ(18)O, δ(11)B). Surface waters and macroalgal tissues were collected along 100-m onshore-offshore transects in areas of high groundwater input for three months at low tide. Water samples from possible N sources were also collected. Mixing model output, along with macroalgal δ(15)N values, indicated that agriculture soil (34%) was the largest anthropogenic N source followed by sewage (27%). These findings suggest that more effective fertilizer application techniques and upgrading sewage treatment systems can minimize N leaching into groundwater. Overall, our multi-stable isotope approach for identifying N sources was successful and may be useful in other coastal waters. PMID:26769108

  2. An in situ approach to detect tree root ecology: linking ground-penetrating radar imaging to isotope-derived water acquisition zones

    PubMed Central

    Isaac, Marney E; Anglaaere, Luke C N

    2013-01-01

    Tree root distribution and activity are determinants of belowground competition. However, studying root response to environmental and management conditions remains logistically challenging. Methodologically, nondestructive in situ tree root ecology analysis has lagged. In this study, we tested a nondestructive approach to determine tree coarse root architecture and function of a perennial tree crop, Theobroma cacao L., at two edaphically contrasting sites (sandstone and phyllite–granite derived soils) in Ghana, West Africa. We detected coarse root vertical distribution using ground-penetrating radar and root activity via soil water acquisition using isotopic matching of δ18O plant and soil signatures. Coarse roots were detected to a depth of 50 cm, however, intraspecifc coarse root vertical distribution was modified by edaphic conditions. Soil δ18O isotopic signature declined with depth, providing conditions for plant–soil δ18O isotopic matching. This pattern held only under sandstone conditions where water acquisition zones were identifiably narrow in the 10–20 cm depth but broader under phyllite–granite conditions, presumably due to resource patchiness. Detected coarse root count by depth and measured fine root density were strongly correlated as were detected coarse root count and identified water acquisition zones, thus validating root detection capability of ground-penetrating radar, but exclusively on sandstone soils. This approach was able to characterize trends between intraspecific root architecture and edaphic-dependent resource availability, however, limited by site conditions. This study successfully demonstrates a new approach for in situ root studies that moves beyond invasive point sampling to nondestructive detection of root architecture and function. We discuss the transfer of such an approach to answer root ecology questions in various tree-based landscapes. PMID:23762519

  3. Reconstructing lake evaporation history and the isotopic composition of precipitation by a coupled δ18O-δ2H biomarker approach

    NASA Astrophysics Data System (ADS)

    Hepp, Johannes; Tuthorn, Mario; Zech, Roland; Mügler, Ines; Schlütz, Frank; Zech, Wolfgang; Zech, Michael

    2015-10-01

    Over the past decades, δ18O and δ2H analyses of lacustrine sediments became an invaluable tool in paleohydrology and paleolimnology for reconstructing the isotopic composition of past lake water and precipitation. However, based on δ18O or δ2H records alone, it can be challenging to distinguish between changes of the precipitation signal and changes caused by evaporation. Here we propose a coupled δ18O-δ2H biomarker approach that provides the possibility to disentangle between these two factors. The isotopic composition of long chain n-alkanes (n-C25, n-C27, n-C29, n-C31) were analyzed in order to establish a 16 ka Late Glacial and Holocene δ2H record for the sediment archive of Lake Panch Pokhari in High Himalaya, Nepal. The δ2Hn-alkane record generally corroborates a previously established δ18Osugar record reporting on high values characterizing the deglaciation and the Older and the Younger Dryas, and low values characterizing the Bølling and the Allerød periods. Since the investigated n-alkane and sugar biomarkers are considered to be primarily of aquatic origin, they were used to reconstruct the isotopic composition of lake water. The reconstructed deuterium excess of lake water ranges from +57‰ to -85‰ and is shown to serve as proxy for the evaporation history of Lake Panch Pokhari. Lake desiccation during the deglaciation, the Older Dryas and the Younger Dryas is affirmed by a multi-proxy approach using the Hydrogen Index (HI) and the carbon to nitrogen ratio (C/N) as additional proxies for lake sediment organic matter mineralization. Furthermore, the coupled δ18O and δ2H approach allows disentangling the lake water isotopic enrichment from variations of the isotopic composition of precipitation. The reconstructed 16 ka δ18Oprecipitation record of Lake Panch Pokhari is well in agreement with the δ18O records of Chinese speleothems and presumably reflects the Indian Summer Monsoon variability.

  4. A stable isotope approach for source apportionment of chlorinated ethene plumes at a complex multi-contamination events urban site.

    PubMed

    Nijenhuis, Ivonne; Schmidt, Marie; Pellegatti, Eleonora; Paramatti, Enrico; Richnow, Hans Hermann; Gargini, Alessandro

    2013-10-01

    The stable carbon isotope composition of chlorinated aliphatic compounds such as chlorinated methanes, ethanes and ethenes was examined as an intrinsic fingerprint for apportionment of sources. A complex field site located in Ferrara (Italy), with more than 50years history of use of chlorinated aliphatic compounds, was investigated in order to assess contamination sources. Several contamination plumes were found in a complex alluvial sandy multi-aquifer system close to the river Po; sources are represented by uncontained former industrial and municipal dump sites as well as by spills at industrial areas. The carbon stable isotope signature allowed distinguishing 2 major sources of contaminants. One source of chlorinated aliphatic contaminants was strongly depleted in ¹³C (<-60‰) suggesting production lines which have used depleted methane for synthesis. The other source had typical carbon isotope compositions of >-40‰ which is commonly observed in recent production of chlorinated solvents. The degradation processes in the plumes could be traced interpreting the isotope enrichment and depletion of parent and daughter compounds, respectively. We demonstrate that, under specific production conditions, namely when highly chlorinated ethenes are produced as by-product during chloromethanes production, ¹³C depleted fingerprinting of contaminants can be obtained and this can be used to track sources and address the responsible party of the pollution in urban areas. PMID:24077332

  5. A multi-isotope approach to characterize acid mine drainage in a hardrock alpine mine, Chaffe Co,Colorado.

    NASA Astrophysics Data System (ADS)

    Cordalis, D.; Williams, M. W.; Wireman, M.; Michel, R. L.; Manning, A.

    2004-12-01

    Here we present information from an innovative suite of stable, radiogenic, and cosmogenic isotopes to better understand groundwater flowpaths and groundwater-surface water interactions in an applied acid mine drainage system. Stable water isotopes, tritium, helium-tritium, sulfur-35, and uranium 234/238 ratios were analyzed from precipitation, groundwater wells, interior mine drainages, and surface waters at the Mary Murphy Mine in Colorado to determine hydrologic transport mechanisms responsible for contaminated zinc releases. Hydrometric measurements suggested a snowmelt-driven pulse of elevated zinc in adit outflow. However, mixing models using stable water isotopes showed a regional groundwater signal in the adit outflow. Tritium values of 11 to 13 TU showed a slight enrichment of bomb spike water compared to snow values of about 9 TU, suggesting an older water source as well. Helium/tritium ratios on a subset of groundwater wells suggested that average residence times of alluvial wells ranged from 2.5 to 8 years. The combination of stable water isotopes and sulfur-35 (half-life of 87 days), showed that zinc-rich waters within the mine derived from infiltrating snowmelt more than a year old. However, measurement of sulfur-35 using low-level scintillation counts was compromised at times by the presence of uranium. We were able to remove the uranium through wet chemistry procedures, improving the accuracy of S-35 measurements. The U234/U238 ratio shows promise in discriminating between acid mine drainage and acid rock drainage. Acid rock drainage shows an unaltered ratio of 1:1, while acid mine drainage is enriched relative to the 1:1 equilibrium ratio. The combination of cosmogenic and stable isotopes within and near the Mary Murphy Mine may provide a useful tool for studying interactions between groundwater and surfacewater in a fractured rock setting. Remediation techniques can be directed more appropriately, and cost effectively, by the characterization of

  6. Isotopic Biogeochemistry

    NASA Technical Reports Server (NTRS)

    Hayes, J. M.

    1985-01-01

    An overview is provided of the biogeochemical research. The funding, productivity, personnel and facilities are reviewed. Some of the technical areas covered are: carbon isotopic records; isotopic studies of banded iron formations; isotope effects in microbial systems; studies of organic compounds in ancient sediments; and development in isotopic geochemistry and analysis.

  7. Can we use the CO2 concentrations determined by continuous-flow isotope ratio mass spectrometry from small samples for the Keeling plot approach?

    PubMed

    Joos, Ottmar; Saurer, Matthias; Heim, Alexander; Hagedorn, Frank; Schmidt, Michael W I; Siegwolf, Rolf T W

    2008-12-01

    A common method to estimate the carbon isotopic composition of soil-respired air is to use Keeling plots (delta(13)C versus 1/CO2 concentration). This approach requires the precise determination of both CO2 concentration ([CO2]), usually measured with an infrared gas analyser (IRGA) in the field, and the analysis of delta(13)C by isotope ratio mass spectrometry (IRMS) in the laboratory. We measured [CO2] with an IRGA in the field (n = 637) and simultaneously collected air samples in 12 mL vials for analysis of the 13C values and the [CO2] using a continuous-flow isotope ratio mass spectrometer. In this study we tested if measurements by the IRGA and IRMS yielded the same results for [CO2], and also investigated the effects of different sample vial preparation methods on the [CO2] measurement and the thereby obtained Keeling plot results. Our results show that IRMS measurements of the [CO2] (during the isotope analysis) were lower than when the [CO2] was measured in the field with the IRGA. This is especially evident when the sample vials were not treated in the same way as the standard vials. From the three different vial preparation methods, the one using N2-filled and overpressurised vials resulted in the best agreement between the IRGA and IRMS [CO2] values. There was no effect on the (13)C-values from the different methods. The Keeling plot results confirmed that the overpressurised vials performed best. We conclude that in the cases where the ranges of [CO2] are large (>300 ppm; in our case it ranged between 70 and 1500 ppm) reliable estimation of the [CO2] with small samples using IRMS is possible for Keeling plot application. We also suggest some guidelines for sample handling in order to achieve proper results. PMID:19009520

  8. Hydrogeochemistry and quality of surface water and groundwater in the vicinity of Lake Monoun, West Cameroon: approach from multivariate statistical analysis and stable isotopic characterization.

    PubMed

    Kamtchueng, Brice T; Fantong, Wilson Y; Wirmvem, Mengnjo J; Tiodjio, Rosine E; Takounjou, Alain F; Ndam Ngoupayou, Jules R; Kusakabe, Minoru; Zhang, Jing; Ohba, Takeshi; Tanyileke, Gregory; Hell, Joseph V; Ueda, Akira

    2016-09-01

    With the use of conventional hydrogeochemical techniques, multivariate statistical analysis, and stable isotope approaches, this paper investigates for the first time surface water and groundwater from the surrounding areas of Lake Monoun (LM), West Cameroon. The results reveal that waters are generally slightly acidic to neutral. The relative abundance of major dissolved species are Ca(2+) > Mg(2+) > Na(+) > K(+) for cations and HCO3 (-) ≫ NO3 (-) > Cl(-) > SO4 (2-) for anions. The main water type is Ca-Mg-HCO3. Observed salinity is related to water-rock interaction, ion exchange process, and anthropogenic activities. Nitrate and chloride have been identified as the most common pollutants. These pollutants are attributed to the chlorination of wells and leaching from pit latrines and refuse dumps. The stable isotopic compositions in the investigated water sources suggest evidence of evaporation before recharge. Four major groups of waters were identified by salinity and NO3 concentrations using the Q-mode hierarchical cluster analysis (HCA). Consistent with the isotopic results, group 1 represents fresh unpolluted water occurring near the recharge zone in the general flow regime; groups 2 and 3 are mixed water whose composition is controlled by both weathering of rock-forming minerals and anthropogenic activities; group 4 represents water under high vulnerability of anthropogenic pollution. Moreover, the isotopic results and the HCA showed that the CO2-rich bottom water of LM belongs to an isolated hydrological system within the Foumbot plain. Except for some springs, groundwater water in the area is inappropriate for drinking and domestic purposes but good to excellent for irrigation. PMID:27535404

  9. Using Stable Isotopes to Link Nutrient Sources in the Everglades and Biological Sinks in Florida Bay: A Biogeochemical Approach to Evaluate Ecosystem Response to Changing Nutrient Regimes

    NASA Astrophysics Data System (ADS)

    Hoare, A. M.; Hollander, D. J.; Heil, C.; Glibert, P.; Murasko, S.; Revilla, M.; Alexander, J.

    2005-05-01

    Anthropogenic influences in South Florida have led to deterioration of its two major ecosystems, the Everglades wetlands and the Florida Bay estuary. Consequently, the Comprehensive Everglades Restoration Plan has been proposed to restore the Everglades ecosystem; however, restoration efforts will likely exert new ecological changes in the Everglades and ultimately Florida Bay. The success of the Florida Everglades restoration depends on our understanding and ability to predict how regional changes in the distribution and composition of dissolved organic and inorganic nutrients will direct the downstream biogeochemical dynamics of Florida Bay. While the transport of freshwater and nutrients to Florida Bay have been studied, much work remains to directly link nutrient dynamics in Florida Bay to nutrient sources in the Everglades. Our study uses stable C and N isotopic measurements of chemical and biological materials from the Everglades and Florida Bay as part of a multi-proxy approach to link nutrient sources in the Everglades to biological sinks in Florida Bay. Isotopic analyses of dissolved and particulate species of water, aquatic vegetation and sedimentary organic matter show that the watersheds within the Everglades are chemically distinct and that these signatures are also reflected in the bay. A large east-west gradient in both carbon and nitrogen (as much as 10‰ for δ15N POM) reflect differing nutrient sources for each region of Florida Bay and is strongly correlated with upstream sources in the Everglades. Isotopic signatures also reflect seasonal relationships associated with wet and dry periods. High C and N measurements of DOM and POM measurements suggest significant influence from waste water in Canal C-111 in eastern Florida Bay, particularly during the dry season. These observations show that nutrients from the Everglades watersheds enter Florida Bay and are important in controlling biogeochemical processes in the bay. This study proves that

  10. Comparing three methods of NEE-flux partitioning from the same grassland ecosystem: the 13C, 18O isotope approach and using simulated Ecosystem respiration

    NASA Astrophysics Data System (ADS)

    Siegwolf, R.; Bantelmann, E.; Saurer, M.; Eugster, W.; Buchmann, N.

    2007-12-01

    As a change in the global climate occurs with increasing temperatures, the Carbon exchange processes of terrestrial ecosystems will change as well. However, it is difficult to quantify the degree to what ecosystem respiration will change relative to the CO2 uptake by photosynthesis. To estimate the carbon sequestration potential of terrestrial vegetation cover it is essential to know both fluxes: ecosystem respiration and the carbon uptake by the vegetation cover. Therefore the net ecosystem exchange of CO2 (NEE) was measured with the eddy covariance method and separated into assimilation and respiration flux. We applied three different approaches, 1) the conventional method, applying the nighttime relationship between soil temperature and NEE for calculating the respiration flux during the day, 2) the use of stable carbon and 3) oxygen isotopes. We compared the results of the three partitioning exercises for a temperate grassland ecosystem in the pre-Alps of Switzerland for four days in June 2004. The assimilation flux derived with the conventional NEE partitioning approach, was best represented at low PAR and low temperatures, in the morning between 5 and 9 am. With increasing temperature and PAR the assimilation for the whole canopy was underestimated. For partitioning NEE via 18O approach, correlations of temperature and radiation with assimilation and respiration flux were significantly higher for the partitioning approach with 18O than for the 13C NEE partitioning. A sensitivity analysis showed the importance of an accurate determination of the equilibrium term θ between CO2 and leaf water δ18O for the NEE partitioning with 18O. For using 13C to partition NEE, the correct magnitude of the 13C fractionation and for the respiration term is essential. The analysis of the data showed that for low light and low morning temperatures the conventional method delivers reasonably good results. When the temperatures exceeded 21°C the isotope approach provided the

  11. Application of a Stable Isotope Approach to Evaluate Impact of Changes in Manufacturing Parameters for an Immediate-Release Tablet.

    PubMed

    Parr, Alan; Badman, Geoff; Bowen, Chester L; Coffin, Mark; Gupta, Manish; Jones, Lori; Kurtinecz, Milena; Naderer, Odin; Travis, Eric; Zhu, John; Patel, Parul

    2016-07-01

    There is continued emphasis from the various worldwide regulatory agencies to ensure that the pharmaceutical industry fully understands the products they are developing. This emphasis is seen via development of quality-by-design (QbD) publications and guidelines generated by the International Committee on Harmonization. The challenge to meet these expectations is primarily associated with the generation of in vivo data (eg, pharmacokinetic data) that is resource intensive. A technique reducing the resources needed to generate this in vivo data permits a more extensive application of QbD principles. This paper presents the application of stable isotopes in pharmacokinetic studies. The data show that the use of stable isotopes can significantly reduce the number of subjects required for a study. This reduction in subjects thus translates into a significant reduction in resources and time needed to generate the required in vivo data to support QbD. PMID:26479497

  12. Sources of organic matter for intertidal consumers on Ascophyllum-shores (SW Iceland): a multi-stable isotope approach

    NASA Astrophysics Data System (ADS)

    Sarà, G.; de Pirro, M.; Romano, C.; Rumolo, P.; Sprovieri, M.; Mazzola, A.

    2007-12-01

    Stable isotopes were used to examine the origin of organic matter in Icelandic Ascophyllum-based habitats, the role of different organic matters in filling intertidal food webs and the food preferences of the most abundant suspension feeders, grazers and predators. We selected three intertidal sites on the SW coast of Iceland where we sampled in early September 2004, organic matter sources (POM, SOM and most abundant primary producers, A. nodosum and F. vesciculosus) and the most abundant macrofauna species (barnacles, mussels, gastropods, sponge and crabs). Even though the primary production ( Ascophyllum-based) was the same at the three study sites, the isotopic composition of common-among-sites organisms varied due to local differences in the origin of available POM and SOM and in food web structures.

  13. Interannual variability in bottom-up processes in the upstream range of the California Current system: An isotopic approach

    NASA Astrophysics Data System (ADS)

    El-Sabaawi, Rana W.; Trudel, Marc; Mackas, David L.; Dower, John F.; Mazumder, Asit

    2012-11-01

    The abundance and composition of zooplankton, fish and seabirds show dramatic interannual variability in temperate coastal regions. Understanding links between this variability and bottom-up processes is an important goal for biological oceanographers. Because zooplankton stable isotopes (δ15N and δ13C) are potentially influenced by variability in phytoplankton nutrient utilization, primary production, and zooplankton trophic structure, they have the potential to elucidate links between bottom-up processes, food web structure, and abundance or species composition of higher trophic levels. Here we measure correlations between zooplankton stable isotopes and oceanographic variables in two time series from the west coast of Vancouver Island, upstream of the California Current upwelling system. We then relate interannual variability in zooplankton stable isotopes to interannual variability in zooplankton species composition. Zooplankton stable isotopes show striking patterns of seasonal, regional and interannual variability. A strong positive correlation between annual averages of zooplankton δ15N and sea-surface temperature is evident in both time series. Zooplankton δ15N is also negatively correlated with interannual anomalies of subarctic copepod biomass in both time series. We propose two different mechanisms to explain these correlations: variability in the strength and direction of horizontal advection, or local fluctuations nutrient availability. We conclude that they are most likely caused by local, temperature-driven fluctuations in nitrate concentrations and primary production. We show that the positive correlation between zooplankton δ15N and temperature is widespread, extending to regions outside of the California Current system. Our findings suggest that interannual variability in zooplankton composition is linked with bottom-up variability in nitrate availability and primary production in the upstream portion of the California Current system. Our

  14. Algebraic approach to the structure of the low-lying states in A ≈100 Ru isotopes

    NASA Astrophysics Data System (ADS)

    Kisyov, S.; Bucurescu, D.; Jolie, J.; Lalkovski, S.

    2016-04-01

    The structure of the low-lying states in the odd- and even-mass A ≈100 Ru isotopes is studied in the framework of two algebraic models. The even-mass Ru nuclei are first described within the interacting boson model 1 (IBM-1). The output of these calculations was then used to calculate the odd-A isotopes within the interacting boson-fermion model 1 (IBFM-1), where a coupling of the odd neutron to the even-even core is considered. The level energies and transition probabilities calculated in the present work are tested against the experimental data. One-nucleon transfer spectroscopic factors as well as electromagnetic moments were also calculated for the odd-A Ru and compared to the experimental values. The transitional character of the isotopes is studied. Most of the low-lying positive-parity states in the odd-A Ru nuclei below 2 MeV are interpreted on the basis of ν d5 /2 and ν g7 /2 configurations. The role of the ν s1 /2 orbital in the nuclear structure of the odd-mass Ru nuclei at low energies is also studied. The negative-parity states are interpreted as ν h11 /2 excitations coupled to the core. The evolution of the IBM-1 and IBFM-1 parameters is discussed.

  15. Isotope Coded Protein Labeling Coupled Immunoprecipitation (ICPL-IP): A Novel Approach for Quantitative Protein Complex Analysis From Native Tissue*

    PubMed Central

    Vogt, Andreas; Fuerholzner, Bettina; Kinkl, Norbert; Boldt, Karsten; Ueffing, Marius

    2013-01-01

    High confidence definition of protein interactions is an important objective toward the understanding of biological systems. Isotope labeling in combination with affinity-based isolation of protein complexes has increased in accuracy and reproducibility, yet, larger organisms—including humans—are hardly accessible to metabolic labeling and thus, a major limitation has been its restriction to small animals, cell lines, and yeast. As composition as well as the stoichiometry of protein complexes can significantly differ in primary tissues, there is a great demand for methods capable to combine the selectivity of affinity-based isolation as well as the accuracy and reproducibility of isotope-based labeling with its application toward analysis of protein interactions from intact tissue. Toward this goal, we combined isotope coded protein labeling (ICPL)1 with immunoprecipitation (IP) and quantitative mass spectrometry (MS). ICPL-IP allows sensitive and accurate analysis of protein interactions from primary tissue. We applied ICPL-IP to immuno-isolate protein complexes from bovine retinal tissue. Protein complexes of immunoprecipitated β-tubulin, a highly abundant protein with known interactors as well as the lowly expressed small GTPase RhoA were analyzed. The results of both analyses demonstrate sensitive and selective identification of known as well as new protein interactions by our method. PMID:23268931

  16. Isotope coded protein labeling coupled immunoprecipitation (ICPL-IP): a novel approach for quantitative protein complex analysis from native tissue.

    PubMed

    Vogt, Andreas; Fuerholzner, Bettina; Kinkl, Norbert; Boldt, Karsten; Ueffing, Marius

    2013-05-01

    High confidence definition of protein interactions is an important objective toward the understanding of biological systems. Isotope labeling in combination with affinity-based isolation of protein complexes has increased in accuracy and reproducibility, yet, larger organisms--including humans--are hardly accessible to metabolic labeling and thus, a major limitation has been its restriction to small animals, cell lines, and yeast. As composition as well as the stoichiometry of protein complexes can significantly differ in primary tissues, there is a great demand for methods capable to combine the selectivity of affinity-based isolation as well as the accuracy and reproducibility of isotope-based labeling with its application toward analysis of protein interactions from intact tissue. Toward this goal, we combined isotope coded protein labeling (ICPL)(1) with immunoprecipitation (IP) and quantitative mass spectrometry (MS). ICPL-IP allows sensitive and accurate analysis of protein interactions from primary tissue. We applied ICPL-IP to immuno-isolate protein complexes from bovine retinal tissue. Protein complexes of immunoprecipitated β-tubulin, a highly abundant protein with known interactors as well as the lowly expressed small GTPase RhoA were analyzed. The results of both analyses demonstrate sensitive and selective identification of known as well as new protein interactions by our method. PMID:23268931

  17. Assessing of distribution, mobility and bioavailability of exogenous Pb in agricultural soils using isotopic labeling method coupled with BCR approach.

    PubMed

    Huang, Zhi-Yong; Xie, Hong; Cao, Ying-Lan; Cai, Chao; Zhang, Zhi

    2014-02-15

    The contamination of Pb in agricultural soils is one of the most important ecological problems, which potentially results in serious health risk on human health through food chain. Hence, the fate of exogenous Pb contaminated in agricultural soils is needed to be deeply explored. By spiking soils with the stable enriched isotopes of (206)Pb, the contamination of exogenous Pb(2+) ions in three agricultural soils sampled from the estuary areas of Jiulong River, China was simulated in the present study, and the distribution, mobility and bioavailability of exogenous Pb in the soils were investigated using the isotopic labeling method coupled with a four-stage BCR (European Community Bureau of Reference) sequential extraction procedure. Results showed that about 60-85% of exogenous Pb was found to distribute in reducible fractions, while the exogenous Pb in acid-extractable fractions was less than 1.0%. After planting, the amounts of exogenous Pb presenting in acid-extractable, reducible and oxidizable fractions in rhizospheric soils decreased by 60-66%, in which partial exogenous Pb was assimilated by plants while most of the metal might transfer downward due to daily watering and applying fertilizer. The results show that the isotopic labeling technique coupled with sequential extraction procedures enables us to explore the distribution, mobility and bioavailability of exogenous Pb contaminated in soils, which may be useful for the further soil remediation. PMID:24412626

  18. Origin of shallow groundwater of Csepel Island (south of Budapest, Hungary, River Danube): isotopic and chemical approach

    NASA Astrophysics Data System (ADS)

    Fórizs, I.; Berecz, T.; Molnár, Z.; Süveges, M.

    2005-11-01

    The shallowest aquifer of the alluvial Csepel Island is used for drinking water supply for Budapest and the surrounding villages. A previous two-dimensional hydraulic model failed to explain many observations; therefore, a three-dimensional hydraulic model was constructed using the software application MODFLOW. Isotopic and hydrogeochemical investigations were carried out during the period 1998 to 2002 in order to provide model data. Four water sources have been identified, having different isotopic (and chemical) characteristics. Danube water is characterized by seasonally varying 18O values: its unweighted mean 18O value is -10.9 for the years 1998 to 2002. The most negative 18O values occur in late spring and summertime. Average tritium content is 20 TU. Infiltrated precipitation has 18O values between -9.0 and -9.5. The average tritium content of the precipitation is 10 TU, and that of infiltrated precipitation must be close to this value and about half that of the Danube. The 18O value of lake water is > -9.0. Its stable isotope composition plots on the right side of the local meteoric water line on the D-18O diagram. Ascending deep groundwater (sampled depth of 20-140 m) has 18O values between -12.0 and -13.5. Its radiocarbon age is between 16 000 and 30 000 years BP, probably infiltrated during and around the last glacial maximum (Würm III) period of the latest glaciation. Copyright

  19. A Lowland Catchment Response to Heavy Agricultural Nitrogen Loads Explained with a Multiple Isotope and Hydrochemical Approach

    NASA Astrophysics Data System (ADS)

    Wexler, S. K.; Hiscock, K. M.; Dennis, P.

    2009-12-01

    East Anglia, UK, is a lowland area of intensive agriculture, producing much of the UK’s arable crops, while also supporting some of Europe’s most sensitive wetland habitats. The River Wensum in East Anglia is a calcareous lowland river with Site of Special Scientific Interest status. Within the catchment Special Areas of Conservation have been designated (EU Habitats Directive). The river supplies the city of Norwich with its drinking water (population 120 000), while downstream of Norwich water from the Wensum flows through the Norfolk Broads, a unique and protected wetland habitat, to enter the North Sea at Great Yarmouth. The Wensum catchment, covering an area of 570 km2, is heavily impacted by agricultural activity with a high nutrient load that affects both the underlying Cretaceous Chalk aquifer and the groundwater-dependent river, which has a base flow index of 0.78. Nitrate concentrations exceed the legal limit in places (up to 85 mg/ L). In this study, river, tributary, drain and groundwater samples from the Wensum catchment were collected over 27 months from February 2007, through all seasons and flow conditions, alongside samples of fertiliser, manure, waste water, precipitation and dry deposition. The nitrogen and oxygen isotopic composition of nitrate was analysed using the denitrifier method to understand nitrogen transport and cycling within the catchment. Water isotopes were used as an additional tracer, with major ion and trace element hydrochemistry. There is evidence of significant natural attenuation of nitrate which occurs in different locations and at varying rates within the catchment hydrology. Baseflow from highly impacted Chalk groundwater in the valley, with the lowest nitrate isotope ratios and highest concentration of catchment waters, is partially denitrified as it passes through a thick gravel hyporheic zone. Nitrate in surface drainage water undergoes assimilation and denitrification as it infiltrates through the soil and

  20. Novel isotopic N, N-Dimethyl Leucine (iDiLeu) Reagents Enable Absolute Quantification of Peptides and Proteins Using a Standard Curve Approach

    NASA Astrophysics Data System (ADS)

    Greer, Tyler; Lietz, Christopher B.; Xiang, Feng; Li, Lingjun

    2015-01-01

    Absolute quantification of protein targets using liquid chromatography-mass spectrometry (LC-MS) is a key component of candidate biomarker validation. One popular method combines multiple reaction monitoring (MRM) using a triple quadrupole instrument with stable isotope-labeled standards (SIS) for absolute quantification (AQUA). LC-MRM AQUA assays are sensitive and specific, but they are also expensive because of the cost of synthesizing stable isotope peptide standards. While the chemical modification approach using mass differential tags for relative and absolute quantification (mTRAQ) represents a more economical approach when quantifying large numbers of peptides, these reagents are costly and still suffer from lower throughput because only two concentration values per peptide can be obtained in a single LC-MS run. Here, we have developed and applied a set of five novel mass difference reagents, isotopic N, N-dimethyl leucine (iDiLeu). These labels contain an amine reactive group, triazine ester, are cost effective because of their synthetic simplicity, and have increased throughput compared with previous LC-MS quantification methods by allowing construction of a four-point standard curve in one run. iDiLeu-labeled peptides show remarkably similar retention time shifts, slightly lower energy thresholds for higher-energy collisional dissociation (HCD) fragmentation, and high quantification accuracy for trypsin-digested protein samples (median errors <15%). By spiking in an iDiLeu-labeled neuropeptide, allatostatin, into mouse urine matrix, two quantification methods are validated. The first uses one labeled peptide as an internal standard to normalize labeled peptide peak areas across runs (<19% error), whereas the second enables standard curve creation and analyte quantification in one run (<8% error).

  1. Novel isotopic N, N-dimethyl leucine (iDiLeu) reagents enable absolute quantification of peptides and proteins using a standard curve approach

    PubMed Central

    Greer, Tyler; Lietz, Christopher B.; Xiang, Feng; Li, Lingjun

    2014-01-01

    Absolute quantification of protein targets using liquid chromatography-mass spectrometry (LC-MS) is a key component of candidate biomarker validation. One popular method combines multiple reaction monitoring (MRM) using a triple quadrupole instrument with stable isotope-labeled standards (SIS) for absolute quantification (AQUA). LC-MRM AQUA assays are sensitive and specific, but they are also expensive due to the cost of synthesizing stable isotope peptide standards. While the chemical modification approach using Mass Differential Tags for Relative and Absolute Quantification (mTRAQ) represents a more economical approach when quantifying large numbers of peptides, these reagents are costly and still suffer from lower throughput because only two concentration values per peptide can be obtained in a single LC-MS run. Here, we have developed and applied a set of five novel mass difference reagents, isotopic N,N-dimethyl leucine (iDiLeu). These labels contain an amine reactive group, triazine ester, are cost effective due to their synthetic simplicity, and have increased throughput compared to previous LC-MS quantification methods by allowing construction of a four-point standard curve in one run. iDiLeu-labeled peptides show remarkably similar retention time shifts, slightly lower energy thresholds for higher-energy collisional dissociation (HCD) fragmentation, and high quantification accuracy for trypsin-digested protein samples (median errors <15%). By spiking in an iDiLeu-labeled neuropeptide, allatostatin, into mouse urine matrix, two quantification methods are validated. The first uses one labeled peptide as an internal standard to normalize labeled peptide peak areas across runs (<19% error) while the second enables standard curve creation and analyte quantification in one run (<8% error). PMID:25377360

  2. Using Novel Approaches in Process-Based Modeling for Interpreting Inter-Annual Variability in Tree Ring Widths, Wood Density Profiles, and Cellulose Isotopic Ratios

    NASA Astrophysics Data System (ADS)

    Friend, A. D.; Babst, F.; Belmecheri, S.; Frank, D. C.; Hacket Pain, A. J.; Hayat, A.; Poulter, B.; Rademacher, T. T.; Trouet, V.

    2015-12-01

    Time series annual of tree ring width, density variation, and oxygen and carbon isotopic compositions have the potential to substantially increase our knowledge of forest responses to environmental variation. However, their interpretation is not straightforward due to the simultaneous influences of a number of confounding factors, including carry-over effects from previous years, variable resource allocation with size, age, and canopy position, species-specific physiologies, and complex interactions between forcings such as temperature, soil moisture, and atmospheric CO2. Here we attempt to tease these factors apart and so substantially improve the interpretability of tree ring archives through the construction and application of novel approaches within a process-based model of individual tree growth. The model incorporates descriptions of xylem cell division, expansion, and secondary wall thickening, apical and lateral meristem activities with internal controls from internal signals, internal carbon storage, and the dynamics of canopy photosynthesis, stomatal movements, evapotranspiration, canopy temperatures, and soil moisture. Alternative treatments of isotopic fractionation and growth controls are evaluated using measured datasets. We demonstrate how this new model approach can be used to assess the information contained in tree rings concerning the influence of increasing atmospheric CO2 over the past century on growth and water use efficiency at a range of sites.

  3. Feeding strategies of four dominant copepod species in Prydz Bay, Antarctica: Insights from a combined fatty acid biomarker and stable isotopic approach

    NASA Astrophysics Data System (ADS)

    Yang, Guang; Li, Chaolun; Guilini, Katja; Peng, Quancai; Wang, Yanqing; Zhang, Ye; Zhang, Yongshan

    2016-08-01

    this combined fatty acid and stable isotopic approach suggest that the dominant copepod species in Prydz Bay, Antarctica, have flexible feeding strategies that vary by food source during the late austral summer.

  4. A Spatially Explicit Dual-Isotope Approach to Map Regions of Plant-Plant Interaction after Exotic Plant Invasion.

    PubMed

    Hellmann, Christine; Werner, Christiane; Oldeland, Jens

    2016-01-01

    Understanding interactions between native and invasive plant species in field settings and quantifying the impact of invaders in heterogeneous native ecosystems requires resolving the spatial scale on which these processes take place. Therefore, functional tracers are needed that enable resolving the alterations induced by exotic plant invasion in contrast to natural variation in a spatially explicit way. 15N isoscapes, i.e., spatially referenced representations of stable nitrogen isotopic signatures, have recently provided such a tracer. However, different processes, e.g. water, nitrogen or carbon cycles, may be affected at different spatial scales. Thus multi-isotope studies, by using different functional tracers, can potentially return a more integrated picture of invader impact. This is particularly true when isoscapes are submitted to statistical methods suitable to find homogeneous subgroups in multivariate data such as cluster analysis. Here, we used model-based clustering of spatially explicit foliar δ15N and δ13C isoscapes together with N concentration of a native indicator species, Corema album, to map regions of influence in a Portuguese dune ecosystem invaded by the N2-fixing Acacia longifolia. Cluster analysis identified regions with pronounced alterations in N budget and water use efficiency in the native species, with a more than twofold increase in foliar N, and δ13C and δ15N enrichment of up to 2‰ and 8‰ closer to the invader, respectively. Furthermore, clusters of multiple functional tracers indicated a spatial shift from facilitation through N addition in the proximity of the invader to competition for resources other than N in close contact. Finding homogeneous subgroups in multi-isotope data by means of model-based cluster analysis provided an effective tool for detecting spatial structure in processes affecting plant physiology and performance. The proposed method can give an objective measure of the spatial extent of influence of

  5. A Spatially Explicit Dual-Isotope Approach to Map Regions of Plant-Plant Interaction after Exotic Plant Invasion

    PubMed Central

    Hellmann, Christine; Werner, Christiane; Oldeland, Jens

    2016-01-01

    Understanding interactions between native and invasive plant species in field settings and quantifying the impact of invaders in heterogeneous native ecosystems requires resolving the spatial scale on which these processes take place. Therefore, functional tracers are needed that enable resolving the alterations induced by exotic plant invasion in contrast to natural variation in a spatially explicit way. 15N isoscapes, i.e., spatially referenced representations of stable nitrogen isotopic signatures, have recently provided such a tracer. However, different processes, e.g. water, nitrogen or carbon cycles, may be affected at different spatial scales. Thus multi-isotope studies, by using different functional tracers, can potentially return a more integrated picture of invader impact. This is particularly true when isoscapes are submitted to statistical methods suitable to find homogeneous subgroups in multivariate data such as cluster analysis. Here, we used model-based clustering of spatially explicit foliar δ15N and δ13C isoscapes together with N concentration of a native indicator species, Corema album, to map regions of influence in a Portuguese dune ecosystem invaded by the N2-fixing Acacia longifolia. Cluster analysis identified regions with pronounced alterations in N budget and water use efficiency in the native species, with a more than twofold increase in foliar N, and δ13C and δ15N enrichment of up to 2‰ and 8‰ closer to the invader, respectively. Furthermore, clusters of multiple functional tracers indicated a spatial shift from facilitation through N addition in the proximity of the invader to competition for resources other than N in close contact. Finding homogeneous subgroups in multi-isotope data by means of model-based cluster analysis provided an effective tool for detecting spatial structure in processes affecting plant physiology and performance. The proposed method can give an objective measure of the spatial extent of influence of

  6. Validation of a single biopsy approach and bolus protein feeding to determine myofibrillar protein synthesis in stable isotope tracer studies in humans

    PubMed Central

    2011-01-01

    Background Minimizing the number of muscle biopsies has important methodological implications and minimizes subject discomfort during a stable isotope amino acid infusion. We aimed to determine the reliability of obtaining a single muscle biopsy for the calculation of muscle protein fractional synthetic rate (FSR) as well as the amount of incorporation time necessary to obtain that biopsy after initiating a stable isotope infusion (Study 1). The calculation of muscle protein FSR requires tracer steady-state during the stable isotope infusion. Therefore, a second aim was to examine if steady-state conditions are compromised in the precursor pools (plasma free or muscle intracellular [IC]) after ingestion of a tracer enriched protein drink and after resistance exercise (Study 2). Methods Sixteen men (23 ± 3 years; BMI = 23.8 ± 2.2 kg/m2, means ± SD) were randomized to perform Study 1 or Study 2 (n = 8, per study). Subjects received a primed, constant infusion of L-[ring-13C6]phenylalanine coupled with muscle biopsies of the vastus lateralis to measure rates of myofibrillar protein synthesis (MPS). Subjects in Study 2 were fed 25 g of whey protein immediately after an acute bout of unilateral resistance exercise. Results There was no difference (P = 0.3) in rates of MPS determined using the steady-state precursor-product equation and determination of tracer incorporation between sequential biopsies 150 min apart or using plasma protein as the baseline enrichment, provided the infusion length was sufficient (230 ± 0.3 min). We also found that adding a modest amount of tracer (4% enriched), calculated based on the measured phenylalanine content of the protein (3.5%) in the drink, did not compromise steady-state conditions (slope of the enrichment curve not different from zero) in the plasma free or, more importantly, the IC pool (both P > 0.05). Conclusions These data demonstrate that the single biopsy approach yields comparable rates of muscle protein synthesis

  7. A new approach to understand methylmercury (CH3Hg) sources and transformation pathways: Compound-specific carbon stable isotope analysis by GC-C-IRMS

    NASA Astrophysics Data System (ADS)

    Baya, P. A.; Point, D.; Amouroux, D. P.; Lebreton, B.; Guillou, G.

    2015-12-01

    Methylmercury (CH3Hg) is a potent neurotoxin which is readily assimilated by organisms and bio-accumulates in aquatic food webs. In humans, consumption of CH3Hg contaminated marine fish is the major route of mercury exposure. However, our understanding of CH3Hg transformation pathways is still incomplete. To close this knowledge gap, we propose to explore the stable carbon isotopic composition (δ13C) of the methyl group of CH3Hg for a better understanding of its sources and transformation mechanisms. The method developed for the determination of the δ13C value of CH3Hg in biological samples involves (i) CH3Hg selective extraction, (ii) derivatization, and (iii) separation by gas chromatography (GC) prior to analysis by combustion isotope ratio mass spectrometry (C-IRMS). We present the figures of merit of this novel method and the first δ13C signatures for certified materials (ERM-CE464, BCR414) and biological samples at different marine trophic levels (i.e., tuna fish, zooplankton). The implications of this new approach to trace the pathways associated with Hg methylation and the mechanisms involved will be discussed.

  8. Ground-water, large-lake interactions in Saginaw Bay, Lake Huron: A geochemical and isotopic approach

    USGS Publications Warehouse

    Kolak, J.J.; Long, D.T.; Matty, J.M.; Larson, G.J.; Sibley, D.F.; Councell, T.B.

    1999-01-01

    Delineating the nature and extent of ground-water inputs is necessary to understand the hydrochemistry of large lakes. Characterizing the interaction between ground water and large lakes (e.g., the Great Lakes) is facilitated by the use of geochemical and isotopic data. In this study, pore waters were extracted from sediment cores collected from Saginaw Bay and the surrounding Saginaw lowland area; the geochemistry and stable isotope signature of these pore waters were used to identify sources for the water and solutes. Cores from Saginaw Bay and the Saginaw lowland area yielded strong vertical gradients in chloride concentrations, suggesting that a high-chloride source is present at depth. The spatial distribution of cores with elevated chloride concentrations corresponds to the regional distribution of chloride in ground water. Most of the Saginaw lowland area cores contain water with significantly lower ??18O values than modern meteoric water, suggesting that the water had been recharged during a much cooler climate. The ??18O values measured in pore waters (from Saginaw Bay cores) containing high chloride concentrations are similar to modern meteoric water; however, values lighter than modern meteoric water are encountered at depth. Chloride:bromide ratios, used to distinguish between different chloride sources, identify formation brine as the likely source for chloride. Transport models indicate that a combination of advection and diffusion is responsible for the observed Saginaw lowland area pore-water profiles. Pore-water profiles in Saginaw Bay sediments are produced primarily by diffusion and require significantly less time to evolve. An upward flux of solutes derived from formation brine could occur elsewhere within the Great Lakes region and significantly affect the geochemical cycling of chloride and other contaminants (e.g., trace metals).

  9. Water isotopes in desiccating lichens

    PubMed Central

    Cuntz, Matthias; Máguas, Cristina; Lakatos, Michael

    2009-01-01

    The stable isotopic composition of water is routinely used as a tracer to study water exchange processes in vascular plants and ecosystems. To date, no study has focussed on isotope processes in non-vascular, poikilohydric organisms such as lichens and bryophytes. To understand basic isotope exchange processes of non-vascular plants, thallus water isotopic composition was studied in various green-algal lichens exposed to desiccation. The study indicates that lichens equilibrate with the isotopic composition of surrounding water vapour. A model was developed as a proof of concept that accounts for the specific water relations of these poikilohydric organisms. The approach incorporates first their variable thallus water potential and second a compartmentation of the thallus water into two isotopically distinct but connected water pools. Moreover, the results represent first steps towards the development of poikilohydric organisms as a recorder of ambient vapour isotopic composition. PMID:19888598

  10. Water isotopes in desiccating lichens.

    PubMed

    Hartard, Britta; Cuntz, Matthias; Máguas, Cristina; Lakatos, Michael

    2009-12-01

    The stable isotopic composition of water is routinely used as a tracer to study water exchange processes in vascular plants and ecosystems. To date, no study has focussed on isotope processes in non-vascular, poikilohydric organisms such as lichens and bryophytes. To understand basic isotope exchange processes of non-vascular plants, thallus water isotopic composition was studied in various green-algal lichens exposed to desiccation. The study indicates that lichens equilibrate with the isotopic composition of surrounding water vapour. A model was developed as a proof of concept that accounts for the specific water relations of these poikilohydric organisms. The approach incorporates first their variable thallus water potential and second a compartmentation of the thallus water into two isotopically distinct but connected water pools. Moreover, the results represent first steps towards the development of poikilohydric organisms as a recorder of ambient vapour isotopic composition. PMID:19888598

  11. A stable-isotope dilution GC-MS approach for the analysis of DFRC (derivatization followed by reductive cleavage) monomers from low-lignin plant materials.

    PubMed

    Schäfer, Judith; Urbat, Felix; Rund, Katharina; Bunzel, Mirko

    2015-03-18

    The derivatization followed by reductive cleavage (DFRC) method is a well-established tool to characterize the lignin composition of plant materials. However, the application of the original procedure, especially the chromatographic determination of the DFRC monomers, is problematic for low-lignin foods. To overcome these problems a modified sample cleanup and a stable-isotope dilution approach were developed and validated. To quantitate the diacetylated DFRC monomers, their corresponding hexadeuterated analogs were synthesized and used as internal standards. By using the selected-ion monitoring mode, matrix-associated interferences can be minimized resulting in higher selectivity and sensitivity. The modified method was applied to four low-lignin samples. Lignin from carrot fibers was classified as guaiacyl-rich whereas the lignins from radish, pear, and asparagus fibers where classified as balanced lignins (guaiacyl/syringyl ratio=1-2). PMID:25727138

  12. Estimation of groundwater residence times in watersheds using the runoff recession hydrograph: Application and comparison with the isotopic approach in two headwater watersheds

    NASA Astrophysics Data System (ADS)

    Vitvar, T.; Burns, D. A.; McDonnell, J. J.

    2001-05-01

    A need exists for a method to estimate groundwater residence time in watersheds that uses readily available data. Current methods require intensive and expensive collection of isotope or other tracer data. We have developed a method for estimation of mean baseflow residence time in watersheds based on runoff recession characteristics in the Winnisook watershed, Catskill Mts, New York, USA, and in the Maimai watershed, New Zealand. We first derived mean transmissivity and storativity of the dynamic subsurface water storage based on calculated runoff recession characteristics, and then we used these to estimate mean baseflow residence time. The two selected watersheds represent two different geomorphic, climatic and hydrological regimes: the Winnisook is an upland forested catchment with 20\\deg mean slope angles, thin soils (<1.0 m) developed in glacial till, 1570 mm annual rainfall and is underlain by permeable layered sedimentary bedrock. The Maimai watershed is a steep humid catchment with 35\\deg mean slope angles, thin soils (<0.5 m), 2700 mm annual rainfall and is underlain by impermeable bedrock. To test the new approach, mean baseflow residence times were calculated using the convolution integral approach relating rainfall to sampled streamflow 18O values. Mean baseflow residence time for the 2 km&^{2}$ Winnisook watershed was about 9 months using both the convolution integral approach and the recession hydrograph approach. The mean baseflow residence time for the 0.3 ha Maimai watershed was 3 months based on the convolution integral approach. The recession hydrograph method yields a slightly different result dependent on the variable shape of the recession hydrograph in this wet climatic regime. This new baseflow recession method may be an alternative to the convolution integral approach, and can delineate dynamic and static reservoirs for solving mixing problems at the watershed scale.

  13. A common parentage for Deccan Continental Flood Basalt and Central Indian Ocean Ridge Basalt? A geochemical and isotopic approach

    NASA Astrophysics Data System (ADS)

    Ray, D.; Misra, S.; Widdowson, M.; Langmuir, C. H.

    2014-04-01

    A comparison of geochemical and Sr-Nd-Pb isotopic compositions for Deccan Continental Flood Basalts (CFBs) and Central Indian Ridge (CIR) Basalts is presented: these data permit assessment of possible parental linkages between the two regions, and comparison of their respective magmatic evolutionary trends in relation to rift-related tectonic events during Gondwana break-up. The present study reveals that Mid-Ocean Ridge Basalt (MORB) from the northern CIR and basalts of Deccan CFB are geochemically dissimilar because of: (1) the Deccan CFB basalts typically show a greater iron-enrichment as compared to the northern CIR MORB, (2) a multi-element spiderdiagram reveals that the Deccan CFBs reveal a more fractionated slope (Ba/YbN > 1), as compared to relatively flat northern CIR MORB (Ba/YbN < 1), (3) there is greater REE fractionation for Deccan CFB than for the northern CIR MORB (i.e., La/YbN ˜ 2.3 and 1 respectively) and (4) substantial variation of compatible-incompatible trace elements and their ratios among the two basalt groups suggests that partial melting is a dominant process for northern CIR MORB, while fractional crystallization was a more important control to the geochemical variation for Deccan CFB. Further, incompatible trace element ratios (Nb/U and Nb/Pb) and radiogenic isotopic data (Sr-Pb-Nd) indicate that the northern CIR MORBs are similar to depleted mantle [and/or normal (N)-MORB], and often lie on a mixing line between depleted mantle and upper continental crust. By contrast, Deccan CFB compositions lie between the lower continental crust and Ocean island basalt. Accordingly, we conclude that the basaltic suites of the northern CIR MORB and Deccan CFB do not share common parentage, and are therefore genetically unrelated to each other. Instead, we infer that the northern CIR MORB were derived from a depleted mantle source contaminated by upper continental crust, probably during the break up of Gondwanaland; the Deccan CFB are more similar to

  14. Denitrification and anammox in tropical aquaculture settlement ponds: an isotope tracer approach for evaluating N2 production.

    PubMed

    Castine, Sarah A; Erler, Dirk V; Trott, Lindsay A; Paul, Nicholas A; de Nys, Rocky; Eyre, Bradley D

    2012-01-01

    Settlement ponds are used to treat aquaculture discharge water by removing nutrients through physical (settling) and biological (microbial transformation) processes. Nutrient removal through settling has been quantified, however, the occurrence of, and potential for microbial nitrogen (N) removal is largely unknown in these systems. Therefore, isotope tracer techniques were used to measure potential rates of denitrification and anaerobic ammonium oxidation (anammox) in the sediment of settlement ponds in tropical aquaculture systems. Dinitrogen gas (N(2)) was produced in all ponds, although potential rates were low (0-7.07 nmol N cm(-3) h(-1)) relative to other aquatic systems. Denitrification was the main driver of N(2) production, with anammox only detected in two of the four ponds. No correlations were detected between the measured sediment variables (total organic carbon, total nitrogen, iron, manganese, sulphur and phosphorous) and denitrification or anammox. Furthermore, denitrification was not carbon limited as the addition of particulate organic matter (paired t-Test; P = 0.350, n = 3) or methanol (paired t-Test; P = 0.744, n = 3) did not stimulate production of N(2). A simple mass balance model showed that only 2.5% of added fixed N was removed in the studied settlement ponds through the denitrification and anammox processes. It is recommended that settlement ponds be used in conjunction with additional technologies (i.e. constructed wetlands or biological reactors) to enhance N(2) production and N removal from aquaculture wastewater. PMID:22962581

  15. Denitrification and Anammox in Tropical Aquaculture Settlement Ponds: An Isotope Tracer Approach for Evaluating N2 Production

    PubMed Central

    Castine, Sarah A.; Erler, Dirk V.; Trott, Lindsay A.; Paul, Nicholas A.; de Nys, Rocky; Eyre, Bradley D.

    2012-01-01

    Settlement ponds are used to treat aquaculture discharge water by removing nutrients through physical (settling) and biological (microbial transformation) processes. Nutrient removal through settling has been quantified, however, the occurrence of, and potential for microbial nitrogen (N) removal is largely unknown in these systems. Therefore, isotope tracer techniques were used to measure potential rates of denitrification and anaerobic ammonium oxidation (anammox) in the sediment of settlement ponds in tropical aquaculture systems. Dinitrogen gas (N2) was produced in all ponds, although potential rates were low (0–7.07 nmol N cm−3 h−1) relative to other aquatic systems. Denitrification was the main driver of N2 production, with anammox only detected in two of the four ponds. No correlations were detected between the measured sediment variables (total organic carbon, total nitrogen, iron, manganese, sulphur and phosphorous) and denitrification or anammox. Furthermore, denitrification was not carbon limited as the addition of particulate organic matter (paired t-Test; P = 0.350, n = 3) or methanol (paired t-Test; P = 0.744, n = 3) did not stimulate production of N2. A simple mass balance model showed that only 2.5% of added fixed N was removed in the studied settlement ponds through the denitrification and anammox processes. It is recommended that settlement ponds be used in conjunction with additional technologies (i.e. constructed wetlands or biological reactors) to enhance N2 production and N removal from aquaculture wastewater. PMID:22962581

  16. Trophic ecology of the pikeperch (Sander lucioperca) in its introduced areas: a stable isotope approach in southwestern France.

    PubMed

    Kopp, Dorothée; Cucherousset, Julien; Syväranta, Jari; Martino, Aurélia; Céréghino, Régis; Santoul, Frédéric

    2009-08-01

    During the last decades, non-native predatory fish species have been largely introduced in European lakes and rivers, calling for detailed information on the trophic ecology of co-existing native and non-native predators. The present study describes the trophic ecology of the introduced pikeperch (Sander lucioperca) in two southwestern French rivers, using stable isotope analysis. Pikeperch could be categorized as a top-predator, and had a significantly higher trophic position (TP, mean+/-SE=4.2+/-0.1) compared to other predatory fish such as the native pike (Esox lucius, TP=3.7+/-0.1) and the introduced European catfish (Silurus glanis, TP=3.8+/-0.1). Most studies of resource use in freshwaters consider predatory fish as ecologically equivalent; however, this study showed that the pikeperch occupied a higher trophic niche compared to other predatory species in the Lot and Tarn rivers (Garonne River basin). This apparent specialization may thus have consequences upon interspecific relationships within the predatory guild and upon the functional organization of biological communities. PMID:19632657

  17. Technical Report: Investigation of Carbon Cycle Processes within a Managed Landscape: An Ecosystem Manipulation and Isotope Tracer Approach

    SciTech Connect

    Griffis, Timothy J; Baker, John M; Billmark, Kaycie

    2009-06-01

    The goal of this research is to provide a better scientific understanding of carbon cycle processes within an agricultural landscape characteristic of the Upper Midwest. This project recognizes the need to study processes at multiple spatial and temporal scales to reduce uncertainty in ecosystem and landscape-scale carbon budgets to provide a sound basis for shaping future policy related to carbon management. Specifically, this project has attempted to answer the following questions: 1. Would the use of cover crops result in a shift from carbon neutral to significant carbon gain in corn-soybean rotation ecosystems of the Upper Midwest? 2. Can stable carbon isotope analyses be used to partition ecosystem respiration into its autotrophic and heterotrophic components? 3. Can this partitioning be used to better understand the fate of crop residues to project changes in the soil carbon reservoir? 4. Are agricultural ecosystems of the Upper Midwest carbon neutral, sinks, or sources? Can the proposed measurement and modeling framework help address landscape-scale carbon budget uncertainties and help guide future carbon management policy?

  18. A new approach for deciphering between single and multiple accumulation events using intra-tooth isotopic variations: Application to the Middle Pleistocene bone bed of Schöningen 13 II-4.

    PubMed

    Julien, Marie-Anne; Rivals, Florent; Serangeli, Jordi; Bocherens, Hervé; Conard, Nicholas J

    2015-12-01

    It is often difficult to differentiate between archaeological bonebeds formed by one event such as a mass kill of a single herd, and those formed by multiple events that occurred over a longer period of time. The application of high temporal resolution studies such as intra-tooth isotopic profiles on archaeological mammal cohorts offers new possibilities for exploring this issue, allowing investigators to decipher between single and multiple accumulation events. We examined (18)O and (13)C isotopic variations from the enamel carbonate of 23 horse third molars from the Middle Pleistocene archaeological site of Schöningen. We employed a new approach to investigate processes of fossil accumulation that uses both bulk and intra-tooth isotopic variations and takes into account animal behavior, age at death and dental development to test the degree of isotopic affinity of animals from the same fossil assemblage. Oxygen and carbon isotope bulk values indicate that the horses from Schöningen 13 II-4 experienced relatively similar climatic and dietary regimes. Inter-individual differences of the bulk values of the horses sampled in the current study present nevertheless inter-individual variability similar to individuals from multi-layered localities. In addition, the intra-tooth isotopic variation of specimens of the same age at death seems to indicate that the studied cohort corresponds to a mix of individuals that recorded both similar and different isotopic histories. Finally, the conditions recorded in the isotopic signal shortly before death (i.e., for teeth not fully mineralized) varied between sampled individuals, suggesting possible differences in the seasonality of death. Considering those results, we discuss the possibility that the horses from Schöningen 13 II-4 correspond to an accumulation of different death events. PMID:25912820

  19. Teasing Foggy Memories out of Pines on the California Channel Islands Using Tree-Ring Width and Stable Isotope Approaches

    NASA Astrophysics Data System (ADS)

    Williams, A. P.; Still, C. J.; Fischer, D. T.; Leavitt, S. W.

    2006-12-01

    The coast of California is home to many rare, endemic conifers and other plants that are not well adapted to the Mediterranean climate that prevails across most of the state. It has long been suggested that coastal pines survived the early-Pleistocene transition to a warmer and drier environment because they benefit from frequent fog and low stratus clouds that provide much needed water inputs and shading during the rainless summer. Here, we report evidence for the importance of this summer cloudiness to Torrey pines (Pinus torreyana) growing on Santa Rosa Island in Channel Islands National Park. We developed a tree-ring width chronology and quantified the relative importance of winter/spring precipitation and summer fog by comparing ring widths to nearby rainfall records and airport cloud-ceiling height data. While winter/spring precipitation explains most of the variation in annual tree-ring width (R2 = 0.592), the frequency of summertime fog correlated significantly and positively with annual ring width for 52 years of available fog data when the effect of winter/spring precipitation was removed (R2 = 0.118). The correlation between fog frequency and ring width decreased sharply when the range of possible cloud-ceiling heights deviated from the habitat range of the Torrey pine stand, emphasizing the importance of direct cloud immersion to these pines. In addition, the relationship between fog frequency and ring width was strongest in the 26 years that had enough winter/spring rainfall to maintain above-average soil moisture throughout the dry summer months (R2 = 0.312). This suggests that Torrey pines have an adaptive growing season length and that summer fog-water inputs are supplemental but not substantial enough to sustain tree growth independently. It may also be suggested that when summer growth does occur, the frequency of summer fog and stratus may govern growing season length. This made a "fog signal" difficult to detect in the stable isotope (carbon and

  20. Isotope separation

    DOEpatents

    Bartlett, Rodney J.; Morrey, John R.

    1978-01-01

    A method and apparatus is described for separating gas molecules containing one isotope of an element from gas molecules containing other isotopes of the same element in which all of the molecules of the gas are at the same electronic state in their ground state. Gas molecules in a gas stream containing one of the isotopes are selectively excited to a different electronic state while leaving the other gas molecules in their original ground state. Gas molecules containing one of the isotopes are then deflected from the other gas molecules in the stream and thus physically separated.

  1. Social Complexification and Pig (Sus scrofa) Husbandry in Ancient China: A Combined Geometric Morphometric and Isotopic Approach.

    PubMed

    Cucchi, Thomas; Dai, Lingling; Balasse, Marie; Zhao, Chunqing; Gao, Jiangtao; Hu, Yaowu; Yuan, Jing; Vigne, Jean-Denis

    2016-01-01

    Pigs have played a major role in the economic, social and symbolic systems of China since the Early Neolithic more than 8,000 years ago. However, the interaction between the history of pig domestication and transformations in Chinese society since then, have not been fully explored. In this paper, we investigated the co-evolution from the earliest farming communities through to the new political and economic models of state-like societies, up to the Chinese Empire, using 5,000 years of archaeological records from the Xiawanggang (XWG) and Xinzhai (XZ) sites (Henan Province). To trace the changes of pig populations against husbandry practices, we combined the geometric morphometric analysis of dental traits with a study of the stable carbon and nitrogen isotope ratios from bone collagen. The domestication process intensified during the Neolithic Yangshao, prompted by greater selective pressure and/or better herd control against wild introgression. After that, pig farming, in XWG, relied on local livestock and a gradual change of husbandry practices overtime. This was characterized by a gentle increase in millet foddering and animal protein intake, until a complete change over to household management during the Han dynasty. The only rupture in this steady trend of husbandry occurred during the Longshan period, with the appearance of small sized and idiosyncratic pigs with specific feeding practices (relying on millet and household scraps). From three exploratory hypothesis, we explored the possibility of anti-elite pig production in XWG during the Longshan period, as a means to resist incorporation into a new economic model promoting intensified domestic production. This exploratory hypothesis is the most suitable to our dataset; however, numerous areas need to be explored further in order to adequately document the role of pigs in the rise of China's complex societies. PMID:27384523

  2. LGM hosing approach to Heinrich Event 1: results and perspectives from data-model integration using water isotopes

    NASA Astrophysics Data System (ADS)

    Roche, Didier M.; Paillard, Didier; Caley, Thibaut; Waelbroeck, Claire

    2014-12-01

    Freshwater hosing has long been used in climate models to represent the perturbation associated with the release of icebergs during Heinrich Events. However, freshwater hosing ignores some of the icebergs-induced feedbacks on climate. It therefore bears the question whether the perturbed climate obtained through classical freshwater hosing experiments is realistic enough to be used as a proxy for a Heinrich Event. Using the fully coupled, water isotope enabled, climate model iLOVECLIM, we conducted a series of freshwater hosing experiments, accounting for the depleted signature of ice-sheet sourced water, under LGM conditions. Using paleoceanographic data, we integrated simulated and measured δ18Ocalcite at the surface and within the ocean column to evaluate whether (i) LGM freshwater hosing is a good proxy for Heinrich Event 1 and whether (ii) different sources for the freshwater in the North Atlantic result in different spatial anomalies that could be used to fingerprint the source of melt water. Results obtained with two sets of experiments indicate that first order simulated δ18Ocalcite anomalies are broadly consistent with the measured anomalies and that a complete shutdown of the thermohaline circulation is not consistent with the reconstructed patterns from foraminiferal calcite. A more detailed statistical analysis of the planktic and benthic δ18Ocalcite anomalies shows that the best experiment is obtained for a severely disturbed thermohaline circulation but not a complete shutdown. With our model sensitivity, this corresponds to a freshwater flux between 0.18 Sv and 0.3 Sv. Our results also indicate a better agreement when the freshwater flux is applied in the Labrador Sea than when directly applied to the Ruddiman Belt.

  3. Social Complexification and Pig (Sus scrofa) Husbandry in Ancient China: A Combined Geometric Morphometric and Isotopic Approach

    PubMed Central

    Balasse, Marie; Zhao, Chunqing; Gao, Jiangtao; Hu, Yaowu; Yuan, Jing; Vigne, Jean-Denis

    2016-01-01

    Pigs have played a major role in the economic, social and symbolic systems of China since the Early Neolithic more than 8,000 years ago. However, the interaction between the history of pig domestication and transformations in Chinese society since then, have not been fully explored. In this paper, we investigated the co-evolution from the earliest farming communities through to the new political and economic models of state-like societies, up to the Chinese Empire, using 5,000 years of archaeological records from the Xiawanggang (XWG) and Xinzhai (XZ) sites (Henan Province). To trace the changes of pig populations against husbandry practices, we combined the geometric morphometric analysis of dental traits with a study of the stable carbon and nitrogen isotope ratios from bone collagen. The domestication process intensified during the Neolithic Yangshao, prompted by greater selective pressure and/or better herd control against wild introgression. After that, pig farming, in XWG, relied on local livestock and a gradual change of husbandry practices overtime. This was characterized by a gentle increase in millet foddering and animal protein intake, until a complete change over to household management during the Han dynasty. The only rupture in this steady trend of husbandry occurred during the Longshan period, with the appearance of small sized and idiosyncratic pigs with specific feeding practices (relying on millet and household scraps). From three exploratory hypothesis, we explored the possibility of anti-elite pig production in XWG during the Longshan period, as a means to resist incorporation into a new economic model promoting intensified domestic production. This exploratory hypothesis is the most suitable to our dataset; however, numerous areas need to be explored further in order to adequately document the role of pigs in the rise of China’s complex societies. PMID:27384523

  4. (Bio)degradation of glyphosate in water-sediment microcosms - A stable isotope co-labeling approach.

    PubMed

    Wang, Shizong; Seiwert, Bettina; Kästner, Matthias; Miltner, Anja; Schäffer, Andreas; Reemtsma, Thorsten; Yang, Qi; Nowak, Karolina M

    2016-08-01

    Glyphosate and its metabolite aminomethylphosphonic acid (AMPA) are frequently detected in water and sediments. Up to date, there are no comprehensive studies on the fate of glyphosate in water-sediment microcosms according to OECD 308 guideline. Stable isotope co-labeled (13)C3(15)N-glyphosate was used to determine the turnover mass balance, formation of metabolites, and formation of residues over a period of 80 days. In the water-sediment system, 56% of the initial (13)C3-glyphosate equivalents was ultimately mineralized, whereas the mineralization in the water system (without sediment) was low, reaching only 2% of (13)C-glyphosate equivalents. This finding demonstrates the key role of sediments in its degradation. Glyphosate was detected below detection limit in the water compartment on day 40, but could still be detected in the sediments, ultimately reaching 5% of (13)C3(15)N-glyphosate equivalents. A rapid increase in (13)C(15)N-AMPA was noted after 10 days, and these transformation products ultimately constituted 26% of the (13)C3-glyphosate equivalents and 79% of the (15)N-glyphosate equivalents. In total, 10% of the (13)C label and 12% of the (15)N label were incorporated into amino acids, indicating no risk bearing biogenic residue formation from (13)C3(15)N-glyphosate. Initially, glyphosate was biodegraded via the sarcosine pathway related to microbial growth, as shown by co-labeled (13)C(15)N-glycine and biogenic residue formation. Later, degradation via AMPA dominated under starvation conditions, as shown by the contents of (13)C-glycine. The presented data provide the first evidence of the speciation of the non-extractable residues as well as the utilization of glyphosate as a carbon and nitrogen source in the water-sediment system. This study also highlights the contribution of both the sarcosine and the AMPA degradation pathways under these conditions. PMID:27140906

  5. Compound-specific stable isotope analysis of pesticides: a combined monitoring and modeling approach to assess pesticide fate and degradation at catchment scale

    NASA Astrophysics Data System (ADS)

    van Breukelen, B. M.; Lutz, S.; Van der Velde, Y.; Elsayed, O. F.; LeFrancq, M.; Payraudeau, S.; Imfeld, G.

    2014-12-01

    Compound-specific stable isotope analysis (CSIA) has proven useful in asessing the fate of groundwater contamination. However, although evidence of diffuse pesticide degradation is crucial, and CSIA methods have been developed for several pesticides, there is a clear lack of field CSIA data of pesticides. This study now presents the first analysis of field CSIA data from a 47-ha agricultural headwater catchment (Alteckendorf, Alsace, France) in the period March to August 2012. Measured stream concentrations of the two investigated chloroacetanilide herbicides (S-metolachlor and acetochlor) were highest (65 μg/L) following an intense rainfall event in the first month after herbicide application. Carbon isotope ratios increased with more than 2 ‰ in 3 months, which indicates the occurrence of herbicide degradation during transport to the stream. Previously, field CSIA data have also been simulated with reactive transport models to evaluate degradation of groundwater contaminants. This study now presents such a model-assisted interpretation of CSIA data for the first time at catchment scale, which aims at exploring the added value of CSIA in monitoring and modelling of pesticide pollution. The conceptual mathematical model succeeded in reproducing the general trend in concentrations and carbon isotope ratios of metolachlor. It also allowed for the quantification of metolachlor degradation (above 70 % during the study period), and yielded a mass export of 1.8 % of the applied pesticide, which is in agreement with the measured pesticide export. The field concentration and CSIA data informed the model building by indicating the importance of overland flow, and slow pesticide degradation in groundwater compared to the upper soil zone. Moreover, incorporation of the field CSIA data into model calibration slightly reduced model uncertainty in the quantification of pesticide degradation. We suggest that a finer temporal CSIA resolution than possible in this study

  6. Carbon transformation and the sources of dissolved inorganic carbonate in sediments of a temperate coastal sea, the Baltic Sea: A stable isotope and modelling approach

    NASA Astrophysics Data System (ADS)

    Lipka, Marko; Liu, Bo; Wegwerth, Antje; Dellwig, Olaf; Winde, Vera; Al-Raei, Abdul M.; Böttcher, Michael E.

    2015-04-01

    Organic matter is mineralized in brackish-marine sediments by microbial activity using predominantly and sulfate as electron acceptors. Under anoxic bottom water conditions, sulfate reduction dominates. Pore water profiles reflect net biogeochemical processes, transformation rates and fluxes of dissolved species across the sediment-water interface. Element fluxes across the sediment-water interface are controlled by different boundary conditions. We present the results of a detailed biogeochemical investigation of interstitial waters from different sediments of the Baltic Sea covering the range of sedimentological and bottom water redox conditions. It was the aim to study the biogeochemical transformation processes and associated element fluxes at the sediment-water-interface and the role of organic matter or methane as potential substrates for microbial activity. Short sediment cores were collected during several research cruises with multicoring devices. Pore waters were analyzed for nutrients, major and trace element concentrations to allow a modelling of net volumetric transformation rates and diffusive element fluxes. Gross sulfate reduction rates were measured in selected cores using incubations with radiotracer. As a tracer for the source of dissolved inorganic carbonate (DIC) the carbon isotope composition was measured. A quantitative interpretation of vertical concentration profiles in the pore waters was performed using different modelling approaches. Element fluxes across the sediment-water interface show a dependence from bottom water redox conditions, sediment compositions, and sedimentation conditions. It is shown that the carbon isotope composition of DIC is a valuable and sensitive parameter in a model-based estimate of the impact of biological and physical mixing of surface sediments. Research is supported by German BMBF within the KÜNO-SECOS project and Leibniz IOW

  7. Decision-tree-model identification of nitrate pollution activities in groundwater: A combination of a dual isotope approach and chemical ions

    NASA Astrophysics Data System (ADS)

    Xue, Dongmei; Pang, Fengmei; Meng, Fanqiao; Wang, Zhongliang; Wu, Wenliang

    2015-09-01

    To develop management practices for agricultural crops to protect against NO3- contamination in groundwater, dominant pollution activities require reliable classification. In this study, we (1) classified potential NO3- pollution activities via an unsupervised learning algorithm based on δ15N- and δ18O-NO3- and physico-chemical properties of groundwater at 55 sampling locations; and (2) determined which water quality parameters could be used to identify the sources of NO3- contamination via a decision tree model. When a combination of δ15N-, δ18O-NO3- and physico-chemical properties of groundwater was used as an input for the k-means clustering algorithm, it allowed for a reliable clustering of the 55 sampling locations into 4 corresponding agricultural activities: well irrigated agriculture (28 sampling locations), sewage irrigated agriculture (16 sampling locations), a combination of sewage irrigated agriculture, farm and industry (5 sampling locations) and a combination of well irrigated agriculture and farm (6 sampling locations). A decision tree model with 97.5% classification success was developed based on SO42 - and Cl- variables. The NO3- and the δ15N- and δ18O-NO3- variables demonstrated limitation in developing a decision tree model as multiple N sources and fractionation processes both resulted in difficulties of discriminating NO3- concentrations and isotopic values. Although only the SO42 - and Cl- were selected as important discriminating variables, concentration data alone could not identify the specific NO3- sources responsible for groundwater contamination. This is a result of comprehensive analysis. To further reduce NO3- contamination, an integrated approach should be set-up by combining N and O isotopes of NO3- with land-uses and physico-chemical properties, especially in areas with complex agricultural activities.

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  9. Decision-tree-model identification of nitrate pollution activities in groundwater: A combination of a dual isotope approach and chemical ions.

    PubMed

    Xue, Dongmei; Pang, Fengmei; Meng, Fanqiao; Wang, Zhongliang; Wu, Wenliang

    2015-09-01

    To develop management practices for agricultural crops to protect against NO3(-) contamination in groundwater, dominant pollution activities require reliable classification. In this study, we (1) classified potential NO3(-) pollution activities via an unsupervised learning algorithm based on δ(15)N- and δ(18)O-NO3(-) and physico-chemical properties of groundwater at 55 sampling locations; and (2) determined which water quality parameters could be used to identify the sources of NO3(-) contamination via a decision tree model. When a combination of δ(15)N-, δ(18)O-NO3(-) and physico-chemical properties of groundwater was used as an input for the k-means clustering algorithm, it allowed for a reliable clustering of the 55 sampling locations into 4 corresponding agricultural activities: well irrigated agriculture (28 sampling locations), sewage irrigated agriculture (16 sampling locations), a combination of sewage irrigated agriculture, farm and industry (5 sampling locations) and a combination of well irrigated agriculture and farm (6 sampling locations). A decision tree model with 97.5% classification success was developed based on SO4(2-) and Cl(-) variables. The NO3(-) and the δ(15)N- and δ(18)O-NO3(-) variables demonstrated limitation in developing a decision tree model as multiple N sources and fractionation processes both resulted in difficulties of discriminating NO3(-) concentrations and isotopic values. Although only the SO4(2-) and Cl(-) were selected as important discriminating variables, concentration data alone could not identify the specific NO3(-) sources responsible for groundwater contamination. This is a result of comprehensive analysis. To further reduce NO3(-) contamination, an integrated approach should be set-up by combining N and O isotopes of NO3(-) with land-uses and physico-chemical properties, especially in areas with complex agricultural activities. PMID:26231989

  10. Evaluation of risks of groundwater quality alteration in Recife urban area (Pernambuco, Brazil) using a multi-isotopic approach.

    NASA Astrophysics Data System (ADS)

    Bertrand, Guillaume; Hirata, Ricardo; Martins, Veridiana; Batista, Jonathan; Bertolo, Reginaldo; Santos, Jeane-Glaucia; Montenegro, Suzanna; Cary, Lise; Petelet-Giraud, Emmanuelle; Pauwels, Hélène; Picot, Géraldine; Braibant, Gilles; Chatton, Eliot; Aquilina, Luc; Labasque, Thierry; Hochreutener, Rebecca; Aurouet, Axel; Franzen, Melissa

    2015-04-01

    The Recife Metropolitan Region (RMR) is a heavily urbanized area located in a estuary zone and over a multi-layered sedimentary system on the Brazilian Atlantic coast. In a context of increasing land use pressures, involving aquifer overexploitation and surface water contamination, and repeated droughts, the identification of groundwater quality risks in RMR is a necessary management requirement. In this perspective, this work focused on the two shallow aquifer systems, named Boa Viagem and Barreiras aquifers, located at the interface between the city (the consumers) and the deeper semi-confined Cretaceous Cabo and Beberibe aquifers. The Holocenic Boa Viagem and Tertiary Barreiras formations conform unconfined sedimentary aquifers, with no more than 80 m of thickness. Cabo is the most important groundwater body for Recife private complementary water supply and it has experienced an intense exploitation in the last three decades. In contrast, Boa Viagem and Barreiras aquifers are more restrictively used, but it is important to understand their water quality degradation,because of hydraulic connections with deeper aquifers, mainly in the littoral part of Recife, where hydraulic potentiometric head of the Cabo aquifer is 60 m below sea water level in some places, with conditions for recharge from shallower aquifers. Through a multi-isotopic characterization (87Sr/86Sr, δ11B, δ18O-SO4, δ34S-SO4) of sampling of 19 wells and 3 surface waters, carried out during two field campaigns with additional geochemical parameters (major ions, noble and major gases, CFC' s and SF6), the spatio-temporal variability of groundwater quality was investigated. The detection of CFC' s, implying a modern recharge component, highlighted the vulnerability of Boa Viagem and Barreiras to surface contaminations. The increasing mineralization and decreasing 87Sr/86Sr from the inland sector wells to the wells located close to the coast or estuary, with higher well and population densities, were

  11. Isotope Cancer Treatment Research at LANL

    SciTech Connect

    Weidner, John; Nortier, Meiring

    2012-04-11

    Los Alamos National Laboratory has produced medical isotopes for diagnostic and imaging purposes for more than 30 years. Now LANL researchers have branched out into isotope cancer treatment studies. New results show that an accelerator-based approach can produce clinical trial quantities of actinium-225, an isotope that has promise as a way to kill tumors without damaging surrounding healthy cells.

  12. Isotope Cancer Treatment Research at LANL

    ScienceCinema

    Weidner, John; Nortier, Meiring

    2014-06-02

    Los Alamos National Laboratory has produced medical isotopes for diagnostic and imaging purposes for more than 30 years. Now LANL researchers have branched out into isotope cancer treatment studies. New results show that an accelerator-based approach can produce clinical trial quantities of actinium-225, an isotope that has promise as a way to kill tumors without damaging surrounding healthy cells.

  13. Lipid biomarker and compound-specific isotope analysis of cave sediments: a new approach to investigating past vegetation change

    NASA Astrophysics Data System (ADS)

    Blyth, A.; Griffiths, T.; Robson, S.

    2009-12-01

    Caves are vital archives for records of terrestrial palaeoenvironmental change, as they form sheltered sediment traps capable of preserving long environmental sequences. Due to their unique role in the landscape, they are also intimately connected to the archaeology and palaeoecology of the parent region. Chemical proxy records preserved in speleothems (chemically precipitated cave deposits) have long been used as a tool in palaeoclimatic research, but clastic sediments deposited by air, water, and breakdown of the surrounding rock also have much to contribute. However, although well researched in a sedimentary context, the geochemical records contained in these deposits, especially organic parameters, have been less well-studied. Here we present the first in-depth study of the organic geochemistry of cave sediment sequences, using samples from two south-east Asian caves, and focusing on plant-derived lipid biomarkers and their associated compound-specific carbon isotope records. The work aimed to establish: whether routine extraction and analysis of compounds was feasible in this context at acceptable sample sizes; whether there was a significant vegetation-derived contribution to the record; whether the depositional mode of the sediment (colluvium, midden, channel fill etc) affects the organic composition; and whether the records show coherent and interpretable variation through time. Two sites were studied: Niah Cave in Borneo, where the sediments recovered are a mixture of colluvium and channel fill and date back to >40 ka; and Hang Boi in Vietnam, where the principal deposit is a Holocene occupation midden dominated by land-snail shells. To recover the lipid fraction 7 g aliquots of freeze-dried sediment were extracted by sonication in 95:5 dichloromethane:methanol. Excess solvent was then removed via rotary evaporation and the extracts derivatised with BF3-Methanol and BSTFA prior to analysis by GC-MS. The lipid extracts contain a range of compounds including

  14. Compound-specific isotope analysis of nitrogen in sedimentary porphyrins: A novel and powerful approach for reconstructing the nitrogen cycle of the past ocean

    NASA Astrophysics Data System (ADS)

    Kashiyama, Y.; Ogawa, N. O.; Chikaraishi, Y.; Grosjean, E.; Summons, R.; Maslen, E.; Grice, K.; Godfrey, L.; Quan, T. M.; Falkowski, P. G.; Kitazato, H.; Ohkouchi, N.

    2008-12-01

    Nitrogen isotopic composition of organic matter produced by primary photosynthetic organisms is crucial information on the state of their nitrogen metabolisms and thus can be a key to understand nitrogen cycle of the past ocean. Unlike the isotopic signal of bulk sedimentary samples, sedimentary porphyrins, the diagenetic products of chlorophylls, directly reflect isotopic compositions of photoautotrophs. We have developed methods for compound-specific nitrogen isotopic analyses of (1) sedimentary porphyrins that were isolated from extractable organic matter and (2) maleimides, chemical degradation products of porphyrins, that were oxidatively extracted from residual organic matter after organic extraction. The former includes (1) isolation and purification of various species of sedimentary porphyrins using high-performance liquid chromatography and (2) determination of nitrogen isotopic compositions of isolated porphyrins on a high- sensitivity elemental analyzer-isotope ratio mass spectrometer (IRMS) system that allows determination of isotopic composition on nanomole-scale nitrogen. The latter method analyzes isotopic composition of maleimides on gas chromatography-combustion-IRMS. Applying these methods, we determine nitrogen isotopic composition of sedimentary porphyrins from various geological samples from the Archean to the Miocene. In the black shales deposited during the Cretaceous Oceanic Anoxic Events, the nitrogen isotopic composition of porphyrins generally ranged from -7 to -4‰, which suggests that the average δ15N value for the entire photoautotrophic community at these times ranged -3 to +1‰ considering the empirical isotopic relationships that the tetrapyrrole nuclei of chlorophylls are depleted in 15N by ~5‰ relative to cell. This finding suggests that nitrogen utilized in the primary production was supplied mainly through N2-fixation by diazotrophic cyanobacteria in these oceans.

  15. A study of the characteristics of karst groundwater circulation based on multi-isotope approach in the Liulin spring area, North China.

    PubMed

    Zang, Hongfei; Zheng, Xiuqing; Qin, Zuodong; Jia, Zhenxing

    2015-01-01

    Due to the significance of karst groundwater for water supply in arid and semi-arid regions, the characteristics of the karst groundwater flow system in the Liulin spring area, North China, are analysed through isotopic tracing (δ(2)H, δ(18)O, δ(13)C and (3)H) and dating approaches ((14)C). The results show that the primary recharge source of karst groundwater is precipitation. Evaporation during dropping and infiltration of rainfall results in a certain offset in the values of δ(2)H and δ(18)O in groundwater samples from the global meteoric water line (GMWL) and the local meteoric water line (LMWL). The altitudes of the recharge region calculated by δ(18)O range from 1280 to 2020 m above sea level, which is consistent with the altitudes of the recharge area. The Liulin spring groups could be regarded as the mixing of groundwater with long and short flow paths at a ratio of 4:1. In the upgradient of the Liulin spring, the groundwater represents modern groundwater features and its [Formula: see text] is mainly derived from dissolution of soil CO(2), while in the downgradient of the Liulin spring, the (14)C age of dissolved inorganic carbon (DIC) in groundwater shows an apparent increase and [Formula: see text] is mainly derived from the dissolution of carbonate rocks. The mean flow rate calculated by (14)C ages of DIC between IS10 and IS12 is 1.23 m/year. PMID:25511581

  16. An economic approach to efficient isotope labeling in insect cells using homemade 15N-, 13C- and 2H-labeled yeast extracts.

    PubMed

    Opitz, Christian; Isogai, Shin; Grzesiek, Stephan

    2015-07-01

    Heterologous expression of proteins in insect cells is frequently used for crystallographic structural studies due to the high yields even for challenging proteins requiring the eukaryotic protein processing capabilities of the host. However for NMR studies, the need for isotope labeling poses extreme challenges in eukaryotic hosts. Here, we describe a robust method to achieve uniform protein (15)N and (13)C labeling of up to 90 % in baculovirus-infected insect cells. The approach is based on the production of labeled yeast extract, which is subsequently supplemented to insect cell growth media. The method also allows deuteration at levels of >60 % without decrease in expression yield. The economic implementation of the labeling procedures into a standard structural biology laboratory environment is described in a step-by-step protocol. Applications are demonstrated for a variety of NMR experiments using the Abelson kinase domain, GFP, and the beta-1 adrenergic receptor as examples. Deuterated expression of the latter provides spectra of very high quality of a eukaryotic G-protein coupled receptor. PMID:26070442

  17. Importance of bacterivory and preferential selection toward diatoms in larvae of Crepidula fornicata (L.) assessed by a dual stable isotope (13C, 15N) labeling approach

    NASA Astrophysics Data System (ADS)

    Leroy, Fanny; Riera, Pascal; Jeanthon, Christian; Edmond, Frédérique; Leroux, Cédric; Comtet, Thierry

    2012-05-01

    In Europe, the gastropod Crepidula fornicata is an invasive species characterized by a long reproductive period (from February to November). Thus, its larvae are exposed to variations in available food sources (in terms of quantity and quality). We aimed to investigate if bacteria could contribute to larval food both in presence or absence of phytoplankton, and to compare these results to seasonal variations of bacteria and phytoplankton abundances at a coastal site in the English Channel. First, ingestion of fluorescent beads of 0.5 to 2 μm diameter, showed that larvae were able to ingest particles of typical bacterial size. Then we used a dual stable isotope labeling approach which consisted in labeling a bacterial pelagic community with 15N and a diatom (Chaetoceros gracilis) culture with 13C, and supplying larvae with 15N-labeled bacteria, 13C-labeled diatoms, and both labeled sources. This technique has, to our knowledge, never been applied to invertebrate larvae. After 24 h of experiment, larvae were significantly enriched in all treatments: + 21.5‰ (∆δ13C) when supplied with diatoms, + 1364‰ (∆δ15N) when supplied with bacteria, and + 24‰ (∆δ13C) and + 135‰ (∆δ15N) when supplied with the two mixed sources. These results indicated that bacteria can contribute to the larval nutrition in C. fornicata, even in the presence of phytoplankton. Our results however suggested that larvae of C. fornicata preferentially used diatoms and showed that the supply of free bacteria did not alter the uptake of diatoms. Considering the seasonal variations of bacteria and phytoplankton abundances at the study site, these results suggested that bacteria may constitute a complementary resource for the larvae of C. fornicata when phytoplankton is abundant and may become a substitute resource when phytoplankton is less available. This approach offers promising perspectives to trace food sources and assess nitrogen and carbon fluxes between planktotrophic larvae

  18. Automated LC-HRMS(/MS) Approach for the Annotation of Fragment Ions Derived from Stable Isotope Labeling-Assisted Untargeted Metabolomics

    PubMed Central

    2014-01-01

    Structure elucidation of biological compounds is still a major bottleneck of untargeted LC-HRMS approaches in metabolomics research. The aim of the present study was to combine stable isotope labeling and tandem mass spectrometry for the automated interpretation of the elemental composition of fragment ions and thereby facilitate the structural characterization of metabolites. The software tool FragExtract was developed and evaluated with LC-HRMS/MS spectra of both native 12C- and uniformly 13C (U-13C)-labeled analytical standards of 10 fungal substances in pure solvent and spiked into fungal culture filtrate of Fusarium graminearum respectively. Furthermore, the developed approach is exemplified with nine unknown biochemical compounds contained in F. graminearum samples derived from an untargeted metabolomics experiment. The mass difference between the corresponding fragment ions present in the MS/MS spectra of the native and U-13C-labeled compound enabled the assignment of the number of carbon atoms to each fragment signal and allowed the generation of meaningful putative molecular formulas for each fragment ion, which in turn also helped determine the elemental composition of the precursor ion. Compared to laborious manual analysis of the MS/MS spectra, the presented algorithm marks an important step toward efficient fragment signal elucidation and structure annotation of metabolites in future untargeted metabolomics studies. Moreover, as demonstrated for a fungal culture sample, FragExtract also assists the characterization of unknown metabolites, which are not contained in databases, and thus exhibits a significant contribution to untargeted metabolomics research. PMID:24965664

  19. Isotopic chirality

    SciTech Connect

    Floss, H.G.

    1994-12-01

    This paper deals with compounds that are chiral-at least in part, due to isotope substitution-and their use in tracing the steric course of enzyme reaction in vitro and in vivo. There are other applications of isotopically chiral compounds (for example, in analyzing the steric course of nonenzymatic reactions and in probing the conformation of biomolecules) that are important but they will not be discussed in this context.

  20. Transuranium isotopes

    SciTech Connect

    Hoffman, D.C.

    1985-12-01

    The needs of the research community for the production of transuranium isotopes, the quantities required, the continuity of production desired, and what a new steady state neutron source would have to provide to satisfy these needs are discussed. Examples of past frontier research which need these isotopes as well as an outline of the proposed Large Einsteinium Activation Program, LEAP, which requires roughly ten times the current production of /sup 254/Es are given. 15 refs., 5 figs., 4 tabs.

  1. A combined U-series, radiocarbon and stable isotope approach for constructing a Pleistocene lake hydrograph: an example from Surprise Valley, California

    NASA Astrophysics Data System (ADS)

    Ibarra, D. E.; Weaver, K. L.; Harris, C.; Maher, K.

    2013-12-01

    Lake records and lake hydrographs provide an integrated record of the hydrologic conditions across a watershed. To provide useful constraints on past changes in climate, robust hydrographs require concordance among multiple geochronologic approaches as well as supporting geochemical and hydrologic evidence. Dating shoreline or near-shore lacustrine carbonates using U-series and radiocarbon methods is one approach for developing the age-elevation constraints to construct lake hydrographs. Geochemical analyses (e.g., stable isotopes, elemental ratios, U-series measurements) of modern waters and sediments, as well as the primary carbonate samples, can be used to assess the potential influence of open-system behavior, detrital Th corrections, or pedogenic overprinting on the calculated ages. Additionally, topographic analyses (e.g., basin pour point, shoreline elevations and sample locations) further constrain the spatial relevance and relationships between sample localities. To evaluate the timing and magnitude of the most recent late Pleistocene lake cycle in Surprise Valley, California, we analyzed 111 sub-samples from 22 laminated shoreline tufa samples using U-series disequilibrium geochronology, and pair these analyses with 15 radiocarbon ages. To further assess the radiocarbon and U-series ages, we measured the stable isotope (δ18O and δ13C) and elemental (Sr/Ca) signatures of the tufa samples, and characterized the range of (234U/238U) observed in the modern waters and playas within the watershed. Topographic analysis verified that Lake Surprise is a closed, inward draining basin, and demonstrated lateral correspondence between samples from the four targeted shoreline sets. Multiple lines of evidence revealed that samples from the highest shorelines are likely from older, higher lake cycles and were influenced by variable amounts of open-system exchange or pedogenic overprinting. The measured U concentrations of ~300 to 1200 ng/g, with (238U/232Th) from ~3 to

  2. Quantification of nitrous oxide (N2O) uptake in boreal forest soils by combining isotopic and microbial approaches

    NASA Astrophysics Data System (ADS)

    Welti, Nina; Siljanen, Henri; Biasi, Christina; Martikainen, Pertti

    2015-04-01

    The amount of nitrous oxide (N2O) produced during denitrification is highly regulated by the function of the last reductase enzyme (nitrous oxide reductase; nosZ) which is known to be inhibited by oxygen, low pH and low temperature, which are typical characteristics of boreal peatlands and some forest soils. Denitrification can be a sink for N2O, if the last step of the process is very efficient. Generally, the N2O sink potential of soils is poorly constrained; while uptake rates were often observed in field studies, the data was rejected as analytical errors or artifacts. This led to the question: when and by which mechanisms does N2O uptake occur in natural boreal forests? In order to answer this question, we established a 15N2O tracer experiment where the production of 15N2 and consumption of 15N2O were quantified in aerobic and anaerobic conditions followed by abundance analyses of genes and transcripts. The laboratory incubations were complemented with molecular approaches which linked the N2O dynamics with individual microbial species and transcriptomics. The abundance of denitrifying functional genes and gene transcripts reducing nitrous oxide (nosZ) were quantified throughout the experiment with sacrificial sampling in order to solve the role of typical and atypical denitrifying populations on N2O consumption. For this study, a Finnish boreal spruce forest and peatland were selected where previous field measurements have revealed negative N2O fluxes (i.e. N2O uptake). Soil horizons were selected in both the organic layer and uppermost mineral soil layer and in the peat layers 0-10 cm and 10-20 cm, where oxygen is limited and N2O uptake occurs at the field scale. 15N-N2O (99 AT %) was added to an initial N2O concentration of 1.7 ppm. All soils were flushed with 100% helium prior to the N2O addition to ensure that the NO3 stocks were reduced, leaving the added N2O as the sole activator of N2O uptake and primary N source. Aerobic N2O uptake was quantified in

  3. Correlated optical and isotopic nanoscopy

    NASA Astrophysics Data System (ADS)

    Saka, Sinem K.; Vogts, Angela; Kröhnert, Katharina; Hillion, François; Rizzoli, Silvio O.; Wessels, Johannes T.

    2014-04-01

    The isotopic composition of different materials can be imaged by secondary ion mass spectrometry. In biology, this method is mainly used to study cellular metabolism and turnover, by pulsing the cells with marker molecules such as amino acids labelled with stable isotopes (15N, 13C). The incorporation of the markers is then imaged with a lateral resolution that can surpass 100 nm. However, secondary ion mass spectrometry cannot identify specific subcellular structures like organelles, and needs to be correlated with a second technique, such as fluorescence imaging. Here, we present a method based on stimulated emission depletion microscopy that provides correlated optical and isotopic nanoscopy (COIN) images. We use this approach to study the protein turnover in different organelles from cultured hippocampal neurons. Correlated optical and isotopic nanoscopy can be applied to a variety of biological samples, and should therefore enable the investigation of the isotopic composition of many organelles and subcellular structures.

  4. Pathways of coupled arsenic and iron cycling in high arsenic groundwater of the Hetao basin, Inner Mongolia, China: an iron isotope approach

    USGS Publications Warehouse

    Guo, Huaming; Liu, Chen; Lu, Hai; Wanty, Richard B.; Wang, Jun; Zhou, Yinzhu

    2013-01-01

    High As groundwater is widely distributed all over the world, which has posed a significant health impact on millions of people. Iron isotopes have recently been used to characterize Fe cycling in aqueous environments, but there is no information on Fe isotope characteristics in the groundwater. Since groundwater As behavior is closely associated with Fe cycling in the aquifers, Fe isotope signatures may help to characterize geochemical processes controlling As concentrations of shallow groundwaters. This study provides the first observation of Fe isotope fractionation in high As groundwater and evaluation of Fe cycling and As behaviors in shallow aquifers in terms of Fe isotope signatures. Thirty groundwater samples were taken for chemical and isotopic analysis in the Hetao basin, Inner Mongolia. Thirty-two sediments were sampled as well from shallow aquifers for Fe isotope analysis. Results showed that groundwater was normally enriched in isotopically light Fe with δ56Fe values between −3.40‰ and 0.58‰ and median of −1.14‰, while heavier δ56Fe values were observed in the sediments (between −1.10‰ and 0.75‰, median +0.36‰). In reducing conditions, groundwaters generally had higher δ56Fe values, in comparison with oxic conditions. High As groundwaters, generally occurring in reducing conditions, had high δ56Fe values, while low As groundwaters normally had low δ56Fe values. Although sediment δ56Fe values were generally independent of lithological conditions, a large variation in sediment δ56Fe values was observed in the oxidation–reduction transition zone. Three pathways were identified for Fe cycling in shallow groundwater, including dissimilatory reduction of Fe(III) oxides, re-adsorption of Fe(II), and precipitation of pyrite and siderite. Dissimilatory reduction of Fe(III) oxides resulted in light δ56Fe values (around −1.0‰) and high As concentration (>50 μg/L) in groundwater in anoxic conditions. Re-adsorption of isotopically

  5. Ca, Sr, O and D isotope approach to defining the chemical evolution of hydrothermal fluids: example from Long Valley, CA, USA

    USGS Publications Warehouse

    Brown, Shaun T.; Kennedy, B. Mack; DePaolo, Donald J.; Hurwitz, Shaul; Evans, William C.

    2013-01-01

    We present chemical and isotopic data for fluids, minerals and rocks from the Long Valley meteoric-hydrothermal system. The samples encompass the presumed hydrothermal upwelling zone in the west moat of the caldera, the Casa Diablo geothermal field, and a series of wells defining a nearly linear, ∼16 km long, west-to-east trend along the likely fluid flow path. Fluid samples were analyzed for the isotopes of water, Sr, and Ca, the concentrations of major cations and anions, alkalinity, and total CO2. Water isotope data conform to trends documented in earlier studies, interpreted as indicating a single hydrothermal fluid mixing with local groundwater. Sr isotopes show subtle changes along the flow path, which requires rapid fluid flow and minimal reaction between the channelized fluids and the wallrocks. Sr and O isotopes are used to calculate fracture spacing using a dual porosity model. Calculated fracture spacing and temperature data for hydrothermal fluids indicate the system is (approximately) at steady-state. Correlated variations among total CO2, and the concentration and isotopic composition of Ca suggest progressive fluid degassing (loss of CO2), which drives calcite precipitation as the fluid flows west-to-east and cools. The shifts in Ca isotopes require that calcite precipitated at temperatures of 150–180 °C is fractionated by ca. −0.3‰ to −0.5‰ relative to aqueous species. Our data are the first evidence that Ca isotopes undergo kinetic fractionation at high temperatures (>100 °C) and can be used to trace calcite precipitation along hydrothermal fluid flow paths.

  6. Systematic Optimization of C-Terminal Amine-Based Isotope Labeling of Substrates Approach for Deep Screening of C-Terminome.

    PubMed

    Zhang, Yang; He, Quanze; Ye, Juanying; Li, Yanhong; Huang, Lin; Li, Qingqing; Huang, Jingnan; Lu, Jianan; Zhang, Xumin

    2015-10-20

    It is well-known that protein C-termini play important roles in various biological processes, and thus the precise characterization of C-termini is essential for fully elucidating protein structures and understanding protein functions. Although many efforts have been made in the field during the latest 2 decades, the progress is still far behind its counterpart, N-termini, and it necessitates more novel or optimized methods. Herein, we report an optimized C-termini identification approach based on the C-terminal amine-based isotope labeling of substrates (C-TAILS) method. We optimized the amidation reaction conditions to achieve higher yield of fully amidated product. We evaluated different carboxyl and amine blocking reagents and found the superior performance of Ac-NHS and ethanolamine. Replacement of dimethylation with acetylation for Lys blocking resulted in the identification of 232 C-terminal peptides in an Escherichia coli sample, about 42% higher than the conventional C-TAILS. A systematic data analysis revealed that the optimized method is unbiased to the number of lysine in peptides, more reproducible and with higher MASCOT scores. Moreover, the introduction of the Single-Charge Ion Inclusion (SCII) method to alleviate the charge deficiency of small peptides allowed an additional 26% increase in identification number. With the optimized method, we identified 481 C-terminal peptides corresponding to 369 C-termini in E. coli in a triplicate experiments using 80 μg each. Our optimized method would benefit the deep screening of C-terminome and possibly help discover some novel C-terminal modifications. Data are available via ProteomeXchange with identifier PXD002409. PMID:26361894

  7. ISOTOPE SEPARATORS

    DOEpatents

    Bacon, C.G.

    1958-08-26

    An improvement is presented in the structure of an isotope separation apparatus and, in particular, is concerned with a magnetically operated shutter associated with a window which is provided for the purpose of enabling the operator to view the processes going on within the interior of the apparatus. The shutier is mounted to close under the force of gravity in the absence of any other force. By closing an electrical circuit to a coil mouated on the shutter the magnetic field of the isotope separating apparatus coacts with the magnetic field of the coil to force the shutter to the open position.

  8. Compound-specific stable isotope analysis of herbicides in stream water: a combined monitoring and modeling approach to assess pollutant degradation at catchment scale

    NASA Astrophysics Data System (ADS)

    Lutz, Stefanie; Van der Velde, Ype; Elsayed, Omniea; Imfeld, Gwenael; Lefrancq, Marie; Payraudeau, Sylvain; Van Breukelen, Boris

    2014-05-01

    Compound-specific stable isotope analysis (CSIA) measures the isotopic composition of a compound, i.e. the relative abundance of light and heavy stable isotopes of an element contained in the compound (e.g. 12C and 13C). As degradation processes may induce a change in isotopic composition (i.e. isotope fractionation), CSIA allows distinguishing degradation from non-destructive processes such as dilution or sorption. CSIA can be combined with model-assisted interpretation to evaluate degradation of contaminants in the environment. Although CSIA methods have also been developed for diffuse pollutants such as pesticides and nitrate, they have not yet been continuously applied in monitoring of diffuse pollution in surface water. Results of a virtual experiment of isotope fractionation at hillslope scale have suggested that CSIA qualifies as a feasible and useful complement to concentration measurements of diffuse pollutants (Lutz et al., 2013). We now present the first continuously measured concentration and carbon CSIA data of herbicides from a 49-ha agricultural catchment (Alsace, France). Stream concentrations of two chloroacetanilide herbicides, i.e. S-metolachlor and acetochlor, were highest (65 μg/L) following an extreme rainfall event in the first month after herbicide application, and subsequently decreased to background concentration level (0.1 μg/L). This decrease was accompanied by an increase of more than 2 ‰ in carbon isotope ratios, which was also observed in surface runoff samples from a plot experiment in the study catchment. The increase of carbon isotope ratios over time indicates the occurrence of herbicide degradation during transport to the stream, and thus demonstrates the advantage of CSIA over pesticide concentration measurements only. Despite providing evidence of herbicide degradation, the field CSIA data do not allow for a comprehensive characterization of herbicide sources, fate and transport in the study catchment. Therefore, we

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

    PubMed Central

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

    2014-01-01

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

  10. Position-specific and clumped stable isotope studies: comparison of the Urey and path-integral approaches for carbon dioxide, nitrous oxide, methane, and propane.

    PubMed

    Webb, Michael A; Miller, Thomas F

    2014-01-16

    We combine path-integral Monte Carlo methods with high-quality potential energy surfaces to compute equilibrium isotope effects in a variety of systems relevant to 'clumped' isotope analysis and isotope geochemistry, including CO2, N2O, methane, and propane. Through a systematic study of heavy-atom isotope-exchange reactions, we quantify and analyze errors that arise in the widely used Urey model for predicting equilibrium constants of isotope-exchange reactions using reduced partition function ratios. These results illustrate that the Urey model relies on a nontrivial cancellation of errors that can shift the apparent equilibrium temperature by as much as 35 K for a given distribution of isotopologues. The calculations reported here provide the same level of precision as the best existing analytical instrumentation, resolving the relative enrichment of certain isotopologues to as little as 0.01‰. These findings demonstrate path-integral methods to be a rigorous and viable alternative to more approximate methods for heavy-atom geochemical applications. PMID:24372450