Science.gov

Sample records for accurate isotopic analysis

  1. Accurate determination of protein methionine oxidation by stable isotope labeling and LC-MS analysis.

    PubMed

    Liu, Hongcheng; Ponniah, Gomathinayagam; Neill, Alyssa; Patel, Rekha; Andrien, Bruce

    2013-12-17

    Methionine (Met) oxidation is a major modification of proteins, which converts Met to Met sulfoxide as the common product. It is challenging to determine the level of Met sulfoxide, because it can be generated during sample preparation and analysis as an artifact. To determine the level of Met sulfoxide in proteins accurately, an isotope labeling and LC-MS peptide mapping method was developed. Met residues in proteins were fully oxidized using hydrogen peroxide enriched with (18)O atoms before sample preparation. Therefore, it was impossible to generate Met sulfoxide as an artifact during sample preparation. The molecular weight difference of 2 Da between Met sulfoxide with the (16)O atom and Met sulfoxide with the (18)O atom was used to differentiate and calculate the level of Met sulfoxide in the sample originally. Using a recombinant monoclonal antibody as a model protein, much lower levels of Met sulfoxide were detected for the two susceptible Met residues with this new method compared to a typical peptide mapping procedure. The results demonstrated efficient elimination of the analytical artifact during LC-MS peptide mapping for the measurement of Met sulfoxide. This method can thus be used when accurate determination of the level of Met sulfoxide is critical.

  2. Accurate determination of human serum transferrin isoforms: Exploring metal-specific isotope dilution analysis as a quantitative proteomic tool.

    PubMed

    Busto, M Estela del Castillo; Montes-Bayón, Maria; Sanz-Medel, Alfredo

    2006-12-15

    Carbohydrate-deficient transferrin (CDT) measurements are considered a reliable marker for chronic alcohol consumption, and its use is becoming extensive in forensic medicine. However, CDT is not a single molecular entity but refers to a group of sialic acid-deficient transferrin isoforms from mono- to trisialotransferrin. Thus, the development of methods to analyze accurately and precisely individual transferrin isoforms in biological fluids such as serum is of increasing importance. The present work illustrates the use of ICPMS isotope dilution analysis for the quantification of transferrin isoforms once saturated with iron and separated by anion exchange chromatography (Mono Q 5/50) using a mobile phase consisting of a gradient of ammonium acetate (0-250 mM) in 25 mM Tris-acetic acid (pH 6.5). Species-specific and species-unspecific spikes have been explored. In the first part of the study, the use of postcolumn addition of a solution of 200 ng mL(-1) isotopically enriched iron (57Fe, 95%) in 25 mM sodium citrate/citric acid (pH 4) permitted the quantification of individual sialoforms of transferrin (from S2 to S5) in human serum samples of healthy individuals as well as alcoholic patients. Second, the species-specific spike method was performed by synthesizing an isotopically enriched standard of saturated transferrin (saturated with 57Fe). The characterization of the spike was performed by postcolumn reverse isotope dilution analysis (this is, by postcolumn addition of a solution of 200 ng mL(-1) natural iron in sodium citrate/citric acid of pH 4). Also, the stability of the transferrin spike was tested during one week with negligible species transformation. Finally, the enriched transferrin was used to quantify the individual isoforms in the same serum samples obtaining results comparative to those of postcolumn isotope dilution and to those previously published in the literature, demonstrating the suitability of both strategies for quantitative transferrin

  3. An in-line micro-pyrolysis system to remove contaminating organic species for precise and accurate water isotope analysis by spectroscopic techniques

    NASA Astrophysics Data System (ADS)

    Panetta, R. J.; Hsiao, G.

    2011-12-01

    Trace levels of organic contaminants such as short alcohols and terpenoids have been shown to cause spectral interference in water isotope analysis by spectroscopic techniques. The result is degraded precision and accuracy in both δD and δ18O for samples such as beverages, plant extracts or slightly contaminated waters. An initial approach offered by manufacturers is post-processing software that analyzes spectral features to identify and flag contaminated samples. However, it is impossible for this software to accurately reconstruct the water isotope signature, thus it is primarily a metric for data quality. Here, we describe a novel in-line pyrolysis system (Micro-Pyrolysis Technology, MPT) placed just prior to the inlet of a cavity ring-down spectroscopy (CRDS) analyzer that effectively removes interfering organic molecules without altering the isotope values of the water. Following injection of the water sample, N2 carrier gas passes the sample through a micro-pyrolysis tube heated with multiple high temperature elements in an oxygen-free environment. The temperature is maintained above the thermal decomposition threshold of most organic compounds (≤ 900 oC), but well below that of water (~2000 oC). The main products of the pyrolysis reaction are non-interfering species such as elemental carbon and H2 gas. To test the efficacy and applicability of the system, waters of known isotopic composition were spiked with varying amounts of common interfering alcohols (methanol, ethanol, propanol, hexanol, trans-2-hexenol, cis-3-hexanol up to 5 % v/v) and common soluble plant terpenoids (carveol, linalool, geraniol, prenol). Spiked samples with no treatment to remove the organics show strong interfering absorption peaks that adversely affect the δD and δ18O values. However, with the MPT in place, all interfering absorption peaks are removed and the water absorption spectrum is fully restored. As a consequence, the δD and δ18O values also return to their original

  4. Isotopic Ratio Outlier Analysis of the S. cerevisiae Metabolome Using Accurate Mass Gas Chromatography/Time-of-Flight Mass Spectrometry: A New Method for Discovery.

    PubMed

    Qiu, Yunping; Moir, Robyn; Willis, Ian; Beecher, Chris; Tsai, Yu-Hsuan; Garrett, Timothy J; Yost, Richard A; Kurland, Irwin J

    2016-03-01

    Isotopic ratio outlier analysis (IROA) is a (13)C metabolomics profiling method that eliminates sample to sample variance, discriminates against noise and artifacts, and improves identification of compounds, previously done with accurate mass liquid chromatography/mass spectrometry (LC/MS). This is the first report using IROA technology in combination with accurate mass gas chromatography/time-of-flight mass spectrometry (GC/TOF-MS), here used to examine the S. cerevisiae metabolome. S. cerevisiae was grown in YNB media, containing randomized 95% (13)C, or 5%(13)C glucose as the single carbon source, in order that the isotopomer pattern of all metabolites would mirror the labeled glucose. When these IROA experiments are combined, the abundance of the heavy isotopologues in the 5%(13)C extracts, or light isotopologues in the 95%(13)C extracts, follows the binomial distribution, showing mirrored peak pairs for the molecular ion. The mass difference between the (12)C monoisotopic and the (13)C monoisotopic equals the number of carbons in the molecules. The IROA-GC/MS protocol developed, using both chemical and electron ionization, extends the information acquired from the isotopic peak patterns for formulas generation. The process that can be formulated as an algorithm, in which the number of carbons, as well as the number of methoximations and silylations are used as search constraints. In electron impact (EI/IROA) spectra, the artifactual peaks are identified and easily removed, which has the potential to generate "clean" EI libraries. The combination of chemical ionization (CI) IROA and EI/IROA affords a metabolite identification procedure that enables the identification of coeluting metabolites, and allowed us to characterize 126 metabolites in the current study. PMID:26820234

  5. High-Precision Tungsten Isotopic Analysis by Multicollection Negative Thermal Ionization Mass Spectrometry Based on Simultaneous Measurement of W and (18)O/(16)O Isotope Ratios for Accurate Fractionation Correction.

    PubMed

    Trinquier, Anne; Touboul, Mathieu; Walker, Richard J

    2016-02-01

    Determination of the (182)W/(184)W ratio to a precision of ± 5 ppm (2σ) is desirable for constraining the timing of core formation and other early planetary differentiation processes. However, WO3(-) analysis by negative thermal ionization mass spectrometry normally results in a residual correlation between the instrumental-mass-fractionation-corrected (182)W/(184)W and (183)W/(184)W ratios that is attributed to mass-dependent variability of O isotopes over the course of an analysis and between different analyses. A second-order correction using the (183)W/(184)W ratio relies on the assumption that this ratio is constant in nature. This may prove invalid, as has already been realized for other isotope systems. The present study utilizes simultaneous monitoring of the (18)O/(16)O and W isotope ratios to correct oxide interferences on a per-integration basis and thus avoid the need for a double normalization of W isotopes. After normalization of W isotope ratios to a pair of W isotopes, following the exponential law, no residual W-O isotope correlation is observed. However, there is a nonideal mass bias residual correlation between (182)W/(i)W and (183)W/(i)W with time. Without double normalization of W isotopes and on the basis of three or four duplicate analyses, the external reproducibility per session of (182)W/(184)W and (183)W/(184)W normalized to (186)W/(183)W is 5-6 ppm (2σ, 1-3 μg loads). The combined uncertainty per session is less than 4 ppm for (183)W/(184)W and less than 6 ppm for (182)W/(184)W (2σm) for loads between 3000 and 50 ng.

  6. Precise and accurate isotopic measurements using multiple-collector ICPMS

    NASA Astrophysics Data System (ADS)

    Albarède, F.; Telouk, Philippe; Blichert-Toft, Janne; Boyet, Maud; Agranier, Arnaud; Nelson, Bruce

    2004-06-01

    New techniques of isotopic measurements by a new generation of mass spectrometers equipped with an inductively-coupled-plasma source, a magnetic mass filter, and multiple collection (MC-ICPMS) are quickly developing. These techniques are valuable because of (1) the ability of ICP sources to ionize virtually every element in the periodic table, and (2) the large sample throughout. However, because of the complex trajectories of multiple ion beams produced in the plasma source whether from the same or different elements, the acquisition of precise and accurate isotopic data with this type of instrument still requires a good understanding of instrumental fractionation processes, both mass-dependent and mass-independent. Although physical processes responsible for the instrumental mass bias are still to be understood more fully, we here present a theoretical framework that allows for most of the analytical limitations to high precision and accuracy to be overcome. After a presentation of unifying phenomenological theory for mass-dependent fractionation in mass spectrometers, we show how this theory accounts for the techniques of standard bracketing and of isotopic normalization by a ratio of either the same or a different element, such as the use of Tl to correct mass bias on Pb. Accuracy is discussed with reference to the concept of cup efficiencies. Although these can be simply calibrated by analyzing standards, we derive a straightforward, very general method to calculate accurate isotopic ratios from dynamic measurements. In this study, we successfully applied the dynamic method to Nd and Pb as examples. We confirm that the assumption of identical mass bias for neighboring elements (notably Pb and Tl, and Yb and Lu) is both unnecessary and incorrect. We further discuss the dangers of straightforward standard-sample bracketing when chemical purification of the element to be analyzed is imperfect. Pooling runs to improve precision is acceptable provided the pooled

  7. Meteoritic Sulfur Isotopic Analysis

    NASA Technical Reports Server (NTRS)

    Thiemens, Mark H.

    1996-01-01

    Funds were requested to continue our program in meteoritic sulfur isotopic analysis. We have recently detected a potential nucleosynthetic sulfur isotopic anomaly. We will search for potential carriers. The documentation of bulk systematics and the possible relation to nebular chemistry and oxygen isotopes will be explored. Analytical techniques for delta(sup 33), delta(sup 34)S, delta(sup 36)S isotopic analysis were improved. Analysis of sub milligram samples is now possible. A possible relation between sulfur isotopes and oxygen was detected, with similar group systematics noted, particularly in the case of aubrites, ureilites and entstatite chondrites. A possible nucleosynthetic excess S-33 has been noted in bulk ureilites and an oldhamite separate from Norton County. High energy proton (approximately 1 GeV) bombardments of iron foils were done to experimentally determine S-33, S-36 spallogenic yields for quantitation of isotopic measurements in iron meteorites. Techniques for measurement of mineral separates were perfected and an analysis program initiated. The systematic behavior of bulk sulfur isotopes will continue to be explored.

  8. Rapid accurate isotopic measurements on boron in boric acid and boron carbide.

    PubMed

    Duchateau, N L; Verbruggen, A; Hendrickx, F; De Bièvre, P

    1986-04-01

    A procedure is described whereby rapid and accurate isotopic measurements can be performed on boron in boric acid and boron carbide after fusion of these compounds with calcium carbonate. It allows the determination of the isotopic composition of boron in boric acid and boron carbide and the direct assay of boron or the (10)B isotope in boron carbide by isotope-dilution mass spectrometry.

  9. Do foraminifera accurately record seawater neodymium isotope composition?

    NASA Astrophysics Data System (ADS)

    Scrivner, Adam; Skinner, Luke; Vance, Derek

    2010-05-01

    Palaeoclimate studies involving the reconstruction of past Atlantic meridional overturning circulation increasingly employ isotopes of neodymium (Nd), measured on a variety of sample media (Frank, 2002). In the open ocean, Nd isotopes are a conservative tracer of water mass mixing and are unaffected by biological and low-temperature fractionation processes (Piepgras and Wasserburg, 1987; Lacan and Jeandel, 2005). For decades, benthic foraminifera have been widely utilised in stable isotope and geochemical studies, but have only recently begun to be exploited as a widely distributed, high-resolution Nd isotope archive (Klevenz et al., 2008), potentially circumventing the difficulties associated with other methods used to recover past deep-water Nd isotopes (Klevenz et al., 2008; Rutberg et al., 2000; Tachikawa et al., 2004). Thus far, a single pilot study (Klevenz et al., 2008) has indicated that core-top sedimentary benthic foraminifera record a Nd isotope composition in agreement with the nearest available bottom seawater data, and has suggested that this archive is potentially useful on both millennial and million-year timescales. Here we present seawater and proximal core-top foraminifer Nd isotope data for samples recovered during the 2008 "RETRO" cruise of the Marion Dufresne. The foraminifer samples comprise a depth-transect spanning 3000m of the water column in the Angola Basin and permit a direct comparison between high-resolution water column and core-top foraminiferal Nd isotope data. We use these data to assess the reliability of both planktonic and benthic foraminifera as recorders of water column neodymium isotope composition. Frank, M., 2002. Radiogenic isotopes: Tracers of past ocean circulation and erosional input, Rev. Geophys., 40 (1), 1001, doi:10.1029/2000RG000094. Klevenz, V., Vance, D., Schmidt, D.N., and Mezger, K., 2008. Neodymium isotopes in benthic foraminifera: Core-top systematics and a down-core record from the Neogene south Atlantic

  10. Final Progress Report: Isotope Identification Algorithm for Rapid and Accurate Determination of Radioisotopes Feasibility Study

    SciTech Connect

    Rawool-Sullivan, Mohini; Bounds, John Alan; Brumby, Steven P.; Prasad, Lakshman; Sullivan, John P.

    2012-04-30

    This is the final report of the project titled, 'Isotope Identification Algorithm for Rapid and Accurate Determination of Radioisotopes,' PMIS project number LA10-HUMANID-PD03. The goal of the work was to demonstrate principles of emulating a human analysis approach towards the data collected using radiation isotope identification devices (RIIDs). It summarizes work performed over the FY10 time period. The goal of the work was to demonstrate principles of emulating a human analysis approach towards the data collected using radiation isotope identification devices (RIIDs). Human analysts begin analyzing a spectrum based on features in the spectrum - lines and shapes that are present in a given spectrum. The proposed work was to carry out a feasibility study that will pick out all gamma ray peaks and other features such as Compton edges, bremsstrahlung, presence/absence of shielding and presence of neutrons and escape peaks. Ultimately success of this feasibility study will allow us to collectively explain identified features and form a realistic scenario that produced a given spectrum in the future. We wanted to develop and demonstrate machine learning algorithms that will qualitatively enhance the automated identification capabilities of portable radiological sensors that are currently being used in the field.

  11. A hydrogen gas-water equilibration method produces accurate and precise stable hydrogen isotope ratio measurements in nutrition studies.

    PubMed

    Wong, William W; Clarke, Lucinda L

    2012-11-01

    Stable hydrogen isotope methodology is used in nutrition studies to measure growth, breast milk intake, and energy requirement. Isotope ratio MS is the best instrumentation to measure the stable hydrogen isotope ratios in physiological fluids. Conventional methods to convert physiological fluids to hydrogen gas (H(2)) for mass spectrometric analysis are labor intensive, require special reagent, and involve memory effect and potential isotope fractionation. The objective of this study was to determine the accuracy and precision of a platinum catalyzed H(2)-water equilibration method for stable hydrogen isotope ratio measurements. Time to reach isotopic equilibrium, day-to-day and week-to-week reproducibility, accuracy, and precision of stable hydrogen isotope ratio measurements by the H(2)-water equilibration method were assessed using a Thermo DELTA V Advantage continuous-flow isotope ratio mass spectrometer. It took 3 h to reach isotopic equilibrium. The day-to-day and week-to-week measurements on water and urine samples with natural abundance and enriched levels of deuterium were highly reproducible. The method was accurate to within 2.8 (o)/oo and reproducible to within 4.0 (o)/oo based on analysis of international references. All the outcome variables, whether in urine samples collected in 10 doubly labeled water studies or plasma samples collected in 26 body water studies, did not differ from those obtained using the reference zinc reduction method. The method produced highly accurate estimation on ad libitum energy intakes, body composition, and water turnover rates. The method greatly reduces the analytical cost and could easily be adopted by laboratories equipped with a continuous-flow isotope ratio mass spectrometer.

  12. A Hydrogen Gas-Water Equilibration Method Produces Accurate and Precise Stable Hydrogen Isotope Ratio Measurements in Nutrition Studies12

    PubMed Central

    Wong, William W.; Clarke, Lucinda L.

    2012-01-01

    Stable hydrogen isotope methodology is used in nutrition studies to measure growth, breast milk intake, and energy requirement. Isotope ratio MS is the best instrumentation to measure the stable hydrogen isotope ratios in physiological fluids. Conventional methods to convert physiological fluids to hydrogen gas (H2) for mass spectrometric analysis are labor intensive, require special reagent, and involve memory effect and potential isotope fractionation. The objective of this study was to determine the accuracy and precision of a platinum catalyzed H2-water equilibration method for stable hydrogen isotope ratio measurements. Time to reach isotopic equilibrium, day-to-day and week-to-week reproducibility, accuracy, and precision of stable hydrogen isotope ratio measurements by the H2-water equilibration method were assessed using a Thermo DELTA V Advantage continuous-flow isotope ratio mass spectrometer. It took 3 h to reach isotopic equilibrium. The day-to-day and week-to-week measurements on water and urine samples with natural abundance and enriched levels of deuterium were highly reproducible. The method was accurate to within 2.8 o/oo and reproducible to within 4.0 o/oo based on analysis of international references. All the outcome variables, whether in urine samples collected in 10 doubly labeled water studies or plasma samples collected in 26 body water studies, did not differ from those obtained using the reference zinc reduction method. The method produced highly accurate estimation on ad libitum energy intakes, body composition, and water turnover rates. The method greatly reduces the analytical cost and could easily be adopted by laboratories equipped with a continuous-flow isotope ratio mass spectrometer. PMID:23014490

  13. Oxygen isotopes in nitrite: Analysis, calibration, and equilibration

    USGS Publications Warehouse

    Casciotti, K.L.; Böhlke, J.K.; McIlvin, M.R.; Mroczkowski, S.J.; Hannon, J.E.

    2007-01-01

    Nitrite is a central intermediate in the nitrogen cycle and can persist in significant concentrations in ocean waters, sediment pore waters, and terrestrial groundwaters. To fully interpret the effect of microbial processes on nitrate (NO3-), nitrite (NO2-), and nitrous oxide (N2O) cycling in these systems, the nitrite pool must be accessible to isotopic analysis. Furthermore, because nitrite interferes with most methods of nitrate isotopic analysis, accurate isotopic analysis of nitrite is essential for correct measurement of nitrate isotopes in a sample that contains nitrite. In this study, nitrite salts with varying oxygen isotopic compositions were prepared and calibrated and then used to test the denitrifier method for nitrite oxygen isotopic analysis. The oxygen isotopic fractionation during nitrite reduction to N2O by Pseudomonas aureofaciens was lower than for nitrate conversion to N2O, while oxygen isotopic exchange between nitrite and water during the reaction was similar. These results enable the extension of the denitrifier method to oxygen isotopic analysis of nitrite (in the absence of nitrate) and correction of nitrate isotopes for the presence of nitrite in "mixed" samples. We tested storage conditions for seawater and freshwater samples that contain nitrite and provide recommendations for accurate oxygen isotopic analysis of nitrite by any method. Finally, we report preliminary results on the equilibrium isotope effect between nitrite and water, which can play an important role in determining the oxygen isotopic value of nitrite where equilibration with water is significant. ?? 2007 American Chemical Society.

  14. Applications of stable isotope analysis in mammalian ecology.

    PubMed

    Walter, W David; Kurle, Carolyn M; Hopkins, John B

    2014-01-01

    In this editorial, we provide a brief introduction and summarize the 10 research articles included in this Special Issue on Applications of stable isotope analysis in mammalian ecology. The first three articles report correction and discrimination factors that can be used to more accurately estimate the diets of extinct and extant mammals using stable isotope analysis. The remaining seven applied research articles use stable isotope analysis to address a variety of wildlife conservation and management questions from the oceans to the mountains.

  15. Trophic hierarchies revealed via amino acid isotopic analysis

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Despite the potential of isotopic methods to illuminate trophic function, accurate estimates of lifetime feeding tendencies have remained elusive. A relatively new approach—referred to as compound-specific isotopic analysis (CSIA)—has emerged, centering on the measurement of 15N:14N ratios in amino ...

  16. Accurate and precise determination of isotopic ratios by MC-ICP-MS: a review.

    PubMed

    Yang, Lu

    2009-01-01

    For many decades the accurate and precise determination of isotope ratios has remained a very strong interest to many researchers due to its important applications in earth, environmental, biological, archeological, and medical sciences. Traditionally, thermal ionization mass spectrometry (TIMS) has been the technique of choice for achieving the highest accuracy and precision. However, recent developments in multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) have brought a new dimension to this field. In addition to its simple and robust sample introduction, high sample throughput, and high mass resolution, the flat-topped peaks generated by this technique provide for accurate and precise determination of isotope ratios with precision reaching 0.001%, comparable to that achieved with TIMS. These features, in combination with the ability of the ICP source to ionize nearly all elements in the periodic table, have resulted in an increased use of MC-ICP-MS for such measurements in various sample matrices. To determine accurate and precise isotope ratios with MC-ICP-MS, utmost care must be exercised during sample preparation, optimization of the instrument, and mass bias corrections. Unfortunately, there are inconsistencies and errors evident in many MC-ICP-MS publications, including errors in mass bias correction models. This review examines "state-of-the-art" methodologies presented in the literature for achievement of precise and accurate determinations of isotope ratios by MC-ICP-MS. Some general rules for such accurate and precise measurements are suggested, and calculations of combined uncertainty of the data using a few common mass bias correction models are outlined.

  17. Isotopic Analysis and Evolved Gases

    NASA Technical Reports Server (NTRS)

    Swindle, Timothy D.; Boynton, William V.; Chutjian, Ara; Hoffman, John H.; Jordan, Jim L.; Kargel, Jeffrey S.; McEntire, Richard W.; Nyquist, Larry

    1996-01-01

    Precise measurements of the chemical, elemental, and isotopic composition of planetary surface material and gases, and observed variations in these compositions, can contribute significantly to our knowledge of the source(s), ages, and evolution of solar system materials. The analyses discussed in this paper are mostly made by mass spectrometers or some other type of mass analyzer, and address three broad areas of interest: (1) atmospheric composition - isotopic, elemental, and molecular, (2) gases evolved from solids, and (3) solids. Current isotopic data on nine elements, mostly from in situ analysis, but also from meteorites and telescopic observations are summarized. Potential instruments for isotopic analysis of lunar, Martian, Venusian, Mercury, and Pluto surfaces, along with asteroid, cometary and icy satellites, surfaces are discussed.

  18. Accurate quantitation of MHC-bound peptides by application of isotopically labeled peptide MHC complexes.

    PubMed

    Hassan, Chopie; Kester, Michel G D; Oudgenoeg, Gideon; de Ru, Arnoud H; Janssen, George M C; Drijfhout, Jan W; Spaapen, Robbert M; Jiménez, Connie R; Heemskerk, Mirjam H M; Falkenburg, J H Frederik; van Veelen, Peter A

    2014-09-23

    Knowledge of the accurate copy number of HLA class I presented ligands is important in fundamental and clinical immunology. Currently, the best copy number determinations are based on mass spectrometry, employing single reaction monitoring (SRM) in combination with a known amount of isotopically labeled peptide. The major drawback of this approach is that the losses during sample pretreatment, i.e. immunopurification and filtration steps, are not well defined and must, therefore, be estimated. In addition, such losses can vary for individual peptides. Therefore, we developed a new approach in which isotopically labeled peptide-MHC monomers (hpMHC) are prepared and added directly after cell lysis, i.e. before the usual sample processing. Using this approach, all losses during sample processing can be accounted for and allows accurate determination of specific MHC class I-presented ligands. Our study pinpoints the immunopurification step as the origin of the rather extreme losses during sample pretreatment and offers a solution to account for these losses. Obviously, this has important implications for accurate HLA-ligand quantitation. The strategy presented here can be used to obtain a reliable view of epitope copy number and thus allows improvement of vaccine design and strategies for immunotherapy.

  19. FAST TRACK COMMUNICATION Accurate estimate of α variation and isotope shift parameters in Na and Mg+

    NASA Astrophysics Data System (ADS)

    Sahoo, B. K.

    2010-12-01

    We present accurate calculations of fine-structure constant variation coefficients and isotope shifts in Na and Mg+ using the relativistic coupled-cluster method. In our approach, we are able to discover the roles of various correlation effects explicitly to all orders in these calculations. Most of the results, especially for the excited states, are reported for the first time. It is possible to ascertain suitable anchor and probe lines for the studies of possible variation in the fine-structure constant by using the above results in the considered systems.

  20. Highly accurate isotope measurements of surface material on planetary objects in situ

    NASA Astrophysics Data System (ADS)

    Riedo, Andreas; Neuland, Maike; Meyer, Stefan; Tulej, Marek; Wurz, Peter

    2013-04-01

    Studies of isotope variations in solar system objects are of particular interest and importance. Highly accurate isotope measurements provide insight into geochemical processes, constrain the time of formation of planetary material (crystallization ages) and can be robust tracers of pre-solar events and processes. A detailed understanding of the chronology of the early solar system and dating of planetary materials require precise and accurate measurements of isotope ratios, e.g. lead, and abundance of trace element. However, such measurements are extremely challenging and until now, they never have been attempted in space research. Our group designed a highly miniaturized and self-optimizing laser ablation time-of-flight mass spectrometer for space flight for sensitive and accurate measurements of the elemental and isotopic composition of extraterrestrial materials in situ. Current studies were performed by using UV radiation for ablation and ionization of sample material. High spatial resolution is achieved by focusing the laser beam to about Ø 20μm onto the sample surface. The instrument supports a dynamic range of at least 8 orders of magnitude and a mass resolution m/Δm of up to 800—900, measured at iron peak. We developed a measurement procedure, which will be discussed in detail, that allows for the first time to measure with the instrument the isotope distribution of elements, e.g. Ti, Pb, etc., with a measurement accuracy and precision in the per mill and sub per mill level, which is comparable to well-known and accepted measurement techniques, such as TIMS, SIMS and LA-ICP-MS. The present instrument performance offers together with the measurement procedure in situ measurements of 207Pb/206Pb ages with the accuracy for age in the range of tens of millions of years. Furthermore, and in contrast to other space instrumentation, our instrument can measure all elements present in the sample above 10 ppb concentration, which offers versatile applications

  1. Line gas sampling system ensures accurate analysis

    SciTech Connect

    Not Available

    1992-06-01

    Tremendous changes in the natural gas business have resulted in new approaches to the way natural gas is measured. Electronic flow measurement has altered the business forever, with developments in instrumentation and a new sensitivity to the importance of proper natural gas sampling techniques. This paper reports that YZ Industries Inc., Snyder, Texas, combined its 40 years of sampling experience with the latest in microprocessor-based technology to develop the KynaPak 2000 series, the first on-line natural gas sampling system that is both compact and extremely accurate. This means the composition of the sampled gas must be representative of the whole and related to flow. If so, relative measurement and sampling techniques are married, gas volumes are accurately accounted for and adjustments to composition can be made.

  2. Analysis of hydrogen isotope mixtures

    DOEpatents

    Villa-Aleman, Eliel

    1994-01-01

    An apparatus and method for determining the concentrations of hydrogen isotopes in a sample. Hydrogen in the sample is separated from other elements using a filter selectively permeable to hydrogen. Then the hydrogen is condensed onto a cold finger or cryopump. The cold finger is rotated as pulsed laser energy vaporizes a portion of the condensed hydrogen, forming a packet of molecular hydrogen. The desorbed hydrogen is ionized and admitted into a mass spectrometer for analysis.

  3. Accurate and Efficient Resolution of Overlapping Isotopic Envelopes in Protein Tandem Mass Spectra

    PubMed Central

    Xiao, Kaijie; Yu, Fan; Fang, Houqin; Xue, Bingbing; Liu, Yan; Tian, Zhixin

    2015-01-01

    It has long been an analytical challenge to accurately and efficiently resolve extremely dense overlapping isotopic envelopes (OIEs) in protein tandem mass spectra to confidently identify proteins. Here, we report a computationally efficient method, called OIE_CARE, to resolve OIEs by calculating the relative deviation between the ideal and observed experimental abundance. In the OIE_CARE method, the ideal experimental abundance of a particular overlapping isotopic peak (OIP) is first calculated for all the OIEs sharing this OIP. The relative deviation (RD) of the overall observed experimental abundance of this OIP relative to the summed ideal value is then calculated. The final individual abundance of the OIP for each OIE is the individual ideal experimental abundance multiplied by 1 + RD. Initial studies were performed using higher-energy collisional dissociation tandem mass spectra on myoglobin (with direct infusion) and the intact E. coli proteome (with liquid chromatographic separation). Comprehensive data at the protein and proteome levels, high confidence and good reproducibility were achieved. The resolving method reported here can, in principle, be extended to resolve any envelope-type overlapping data for which the corresponding theoretical reference values are available. PMID:26439836

  4. Fast and accurate dating of nuclear events using La-140/Ba-140 isotopic activity ratio.

    PubMed

    Yamba, Kassoum; Sanogo, Oumar; Kalinowski, Martin B; Nikkinen, Mika; Koulidiati, Jean

    2016-06-01

    This study reports on a fast and accurate assessment of zero time of certain nuclear events using La-140/Ba-140 isotopic activity ratio. For a non-steady nuclear fission reaction, the dating is not possible. For the hypothesis of a nuclear explosion and for a release from a steady state nuclear fission reaction the zero-times will differ. This assessment is fast, because we propose some constants that can be used directly for the calculation of zero time and its upper and lower age limits. The assessment is accurate because of the calculation of zero time using a mathematical method, namely the weighted least-squares method, to evaluate an average value of the age of a nuclear event. This was done using two databases that exhibit differences between the values of some nuclear parameters. As an example, the calculation method is applied for the detection of radionuclides La-140 and Ba-140 in May 2010 at the radionuclides station JPP37 (Okinawa Island, Japan).

  5. Molecular Isotopic Distribution Analysis (MIDAs) with Adjustable Mass Accuracy

    NASA Astrophysics Data System (ADS)

    Alves, Gelio; Ogurtsov, Aleksey Y.; Yu, Yi-Kuo

    2014-01-01

    In this paper, we present Molecular Isotopic Distribution Analysis (MIDAs), a new software tool designed to compute molecular isotopic distributions with adjustable accuracies. MIDAs offers two algorithms, one polynomial-based and one Fourier-transform-based, both of which compute molecular isotopic distributions accurately and efficiently. The polynomial-based algorithm contains few novel aspects, whereas the Fourier-transform-based algorithm consists mainly of improvements to other existing Fourier-transform-based algorithms. We have benchmarked the performance of the two algorithms implemented in MIDAs with that of eight software packages (BRAIN, Emass, Mercury, Mercury5, NeutronCluster, Qmass, JFC, IC) using a consensus set of benchmark molecules. Under the proposed evaluation criteria, MIDAs's algorithms, JFC, and Emass compute with comparable accuracy the coarse-grained (low-resolution) isotopic distributions and are more accurate than the other software packages. For fine-grained isotopic distributions, we compared IC, MIDAs's polynomial algorithm, and MIDAs's Fourier transform algorithm. Among the three, IC and MIDAs's polynomial algorithm compute isotopic distributions that better resemble their corresponding exact fine-grained (high-resolution) isotopic distributions. MIDAs can be accessed freely through a user-friendly web-interface at http://www.ncbi.nlm.nih.gov/CBBresearch/Yu/midas/index.html.

  6. Investigation of mass dependence effects for the accurate determination of molybdenum isotope amount ratios by MC-ICP-MS using synthetic isotope mixtures.

    PubMed

    Malinovsky, Dmitry; Dunn, Philip J H; Petrov, Panayot; Goenaga-Infante, Heidi

    2015-01-01

    Methodology for absolute Mo isotope amount ratio measurements by multicollector inductively coupled plasma-mass spectrometry (MC-ICP-MS) using calibration with synthetic isotope mixtures (SIMs) is presented. For the first time, synthetic isotope mixtures prepared from seven commercially available isotopically enriched molybdenum metal powders ((92)Mo, (94)Mo, (95)Mo, (96)Mo, (97)Mo, (98)Mo, and (100)Mo) are used to investigate whether instrumental mass discrimination of Mo isotopes in MC-ICP-MS is consistent with mass-dependent isotope distribution. The parent materials were dissolved and mixed as solutions to obtain mixtures with accurately known isotope amount ratios. The level of elemental impurities in the isotopically enriched molybdenum metal powders was quantified by ICP-MS by using both high-resolution and reaction cell instruments to completely resolve spectral interferences. The Mo isotope amount ratio values with expanded uncertainty (k = 2), determined by MC-ICP-MS for a high-purity Mo rod from Johnson Matthey, were as follows: (92)Mo/(95)Mo = 0.9235(9), (94)Mo/(95)Mo = 0.5785(8), (96)Mo/(95)Mo = 1.0503(9), (97)Mo/(95)Mo = 0.6033(6), (98)Mo/(95)Mo = 1.5291(20), and (100)Mo/(95)Mo = 0.6130(7). A full uncertainty budget for the measurements is presented which shows that the largest contribution to the uncertainty budget comes from correction for elemental impurities (∼51%), followed by the contribution from weighing operations (∼26 %). The atomic weight of molybdenum was calculated to be 95.947(2); the uncertainty in parentheses is expanded uncertainty with the coverage factor of 2. A particular advantage of the developed method is that calibration factors for all six Mo isotope amount ratios, involving the (95)Mo isotope, were experimentally determined. This allows avoiding any assumption on mass-dependent isotope fractions in MC-ICP-MS, inherent to the method of double spike previously used for Mo isotope amount ratio

  7. Accurate and precise Pb isotope ratio measurements in environmental samples by MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    Weiss, Dominik J.; Kober, Bernd; Dolgopolova, Alla; Gallagher, Kerry; Spiro, Baruch; Le Roux, Gaël; Mason, Thomas F. D.; Kylander, Malin; Coles, Barry J.

    2004-04-01

    Analytical protocols for accurate and precise Pb isotope ratio determinations in peat, lichen, vegetable, chimney dust, and ore-bearing granites using MC-ICP-MS and their application to environmental studies are presented. Acid dissolution of various matrix types was achieved using high temperature/high pressure microwave and hot plate digestion procedures. The digests were passed through a column packed with EiChrom Sr-resin employing only hydrochloric acid and one column passage. This simplified column chemistry allowed high sample throughput. Typically, internal precisions for approximately 30 ng Pb were below 100 ppm (+/-2[sigma]) on all Pb ratios in all matrices. Thallium was employed to correct for mass discrimination effects and the achieved accuracy was below 80 ppm for all ratios. This involved an optimization procedure for the 205Tl/203Tl ratio using least square fits relative to certified NIST-SRM 981 Pb values. The long-term reproducibility (+/-2[sigma]) for the NIST-SRM 981 Pb standard over a 5-month period (35 measurements) was better than 350 ppm for all ratios. Selected ore-bearing granites were measured with TIMS and MC-ICP-MS and showed good correlation (e.g., r=0.999 for 206Pb/207Pb ratios, slope=0.996, n=13). Mass bias and signal intensities of Tl spiked into natural (after matrix separation) and in synthetic samples did not differ significantly, indicating that any residual components of the complex peat and lichen matrix did not influence mass bias correction. Environmental samples with very different matrices were analyzed during two different studies: (i) lichens, vegetables, and chimney dust around a Cu smelter in the Urals, and (ii) peat samples from an ombrotrophic bog in the Faroe Islands. The presented procedure for sample preparation, mass spectrometry, and data processing tools resulted in accurate and precise Pb isotope data that allowed the reliable differentiation and identification of Pb sources with variations as small as 0

  8. Calcium isotope analysis by mass spectrometry.

    PubMed

    Boulyga, Sergei F

    2010-01-01

    The variations in the isotopic composition of calcium caused by fractionation in heterogeneous systems and by nuclear reactions can provide insight into numerous biological, geological, and cosmic processes, and therefore isotopic analysis finds a wide spectrum of applications in cosmo- and geochemistry, paleoclimatic, nutritional, and biomedical studies. The measurement of calcium isotopic abundances in natural samples has challenged the analysts for more than three decades. Practically all Ca isotopes suffer from significant isobaric interferences, whereas low-abundant isotopes can be particularly affected by neighboring major isotopes. The extent of natural variations of stable isotopes appears to be relatively limited, and highly precise techniques are required to resolve isotopic effects. Isotope fractionation during sample preparation and measurements and instrumental mass bias can significantly exceed small isotope abundance variations in samples, which have to be investigated. Not surprisingly, a TIMS procedure developed by Russell et al. (Russell et al., 1978. Geochim Cosmochim Acta 42: 1075-1090) for Ca isotope measurements was considered as revolutionary for isotopic measurements in general, and that approach is used nowadays (with small modifications) for practically all isotopic systems and with different mass spectrometric techniques. Nevertheless, despite several decades of calcium research and corresponding development of mass spectrometers, the available precision and accuracy is still not always sufficient to achieve the challenging goals. The present article discusses figures of merits of presently used analytical methods and instrumentation, and attempts to critically assess their limitations. In Sections 2 and 3, mass spectrometric methods applied to precise stable isotope analysis and to the determination of (41)Ca are described. Section 4 contains a short summary of selected applications, and includes tracer experiments and the potential use

  9. Autonomous Instrumentation for Fast, Continuous and Accurate Isotopic Measurements of Water Vapor (δ18O, δ 2H, H2O) in the Field

    NASA Astrophysics Data System (ADS)

    Liem, J. S.; Dong, F.; Owano, T. G.; Baer, D. S.

    2010-12-01

    Stable isotopes of water vapor are powerful tracers to investigate the hydrological cycle and ecological processes. Therefore, continuous, in-situ and accurate measurements of δ18O and δ2H are critical to advance the understanding of water-cycle dynamics worldwide. Furthermore, the combination of meteorological techniques and high-frequency isotopic water measurements can provide detailed time-resolved information on the eco-physiological performance of plants and enable improved understanding of water fluxes at ecosystem scales. In this work, we present recent development and field deployment of a novel Water Vapor Isotope Measurement System (WVIMS) capable of simultaneous in situ measurements of δ18O and δ2H and water mixing ratio (H2O) with high precision, accuracy and speed (up to 10 Hz measurement rate). The WVIMS consists of an Analyzer (Water Vapor Isotope Analyzer), based on cavity enhanced laser absorption spectroscopy, and a Standard Source (Water Vapor Isotope Standard Source), based on quantitative evaporation of a liquid water standard (with known isotopic content), and operates in a dual-inlet configuration. The WVIMS automatically controls the entire sample and data collection, data analysis and calibration process to allow for continuous, autonomous unattended long-term operation. The WVIMS has been demonstrated for accurate (i.e. fully calibrated) measurements ranging from 500 ppmv (typical of arctic environments) to over 30,000 ppmv (typical of tropical environments) in air. Dual-inlet operation, which involves regular calibration with isotopic water vapor reference standards, essentially eliminates measurement drift, ensures data reliability, and allows operation over an extremely wide ambient temperature range (5-45C). This presentation will include recent measurements recorded using the WVIMS in plant growth chambers and in arctic environments. The availability of this new instrumentation provides new opportunities for detailed continuous

  10. Accurate determination of selected pesticides in soya beans by liquid chromatography coupled to isotope dilution mass spectrometry.

    PubMed

    Huertas Pérez, J F; Sejerøe-Olsen, B; Fernández Alba, A R; Schimmel, H; Dabrio, M

    2015-05-01

    A sensitive, accurate and simple liquid chromatography coupled with mass spectrometry method for the determination of 10 selected pesticides in soya beans has been developed and validated. The method is intended for use during the characterization of selected pesticides in a reference material. In this process, high accuracy and appropriate uncertainty levels associated to the analytical measurements are of utmost importance. The analytical procedure is based on sample extraction by the use of a modified QuEChERS (quick, easy, cheap, effective, rugged, safe) extraction and subsequent clean-up of the extract with C18, PSA and Florisil. Analytes were separated on a C18 column using gradient elution with water-methanol/2.5 mM ammonium acetate mobile phase, and finally identified and quantified by triple quadrupole mass spectrometry in the multiple reaction monitoring mode (MRM). Reliable and accurate quantification of the analytes was achieved by means of stable isotope-labelled analogues employed as internal standards (IS) and calibration with pure substance solutions containing both, the isotopically labelled and native compounds. Exceptions were made for thiodicarb and malaoxon where the isotopically labelled congeners were not commercially available at the time of analysis. For the quantification of those compounds methomyl-(13)C2(15)N and malathion-D10 were used respectively. The method was validated according to the general principles covered by DG SANCO guidelines. However, validation criteria were set more stringently. Mean recoveries were in the range of 86-103% with RSDs lower than 8.1%. Repeatability and intermediate precision were in the range of 3.9-7.6% and 1.9-8.7% respectively. LODs were theoretically estimated and experimentally confirmed to be in the range 0.001-0.005 mg kg(-1) in the matrix, while LOQs established as the lowest spiking mass fractionation level were in the range 0.01-0.05 mg kg(-1). The method reliably identifies and quantifies the

  11. Pitfalls in compound-specific isotope analysis of environmental samples.

    PubMed

    Blessing, Michaela; Jochmann, Maik A; Schmidt, Torsten C

    2008-01-01

    In the last decade compound-specific stable isotope analysis (CSIA) has evolved as a valuable technique in the field of environmental science, especially in contaminated site assessment. Instrumentation and methods exist for highly precise measurements of the isotopic composition of organic contaminants even in a very low concentration range. Nevertheless, the determination of precise and accurate isotope data of environmental samples can be a challenge. Since CSIA is gaining more and more popularity in the assessment of in situ biodegradation of organic contaminants, an increasing number of authorities and environmental consulting offices are interested in the application of the method for contaminated site remediation. Because of this, it is important to demonstrate the problems and limitations associated with compound-specific isotope measurements of environmental samples. In this review, potential pitfalls of the analytical procedure are critically discussed and strategies to avoid possible sources of error are provided. In order to maintain the analytical quality and to ensure the basis for reliable stable isotope data, recommendations on groundwater sampling, and sample preservation and storage are given. Important aspects of sample preparation and preconcentration techniques to improve sensitivity are highlighted. Problems related to chromatographic resolution and matrix interference are discussed that have to be considered in order to achieve accurate gas chromatography/isotope ratio mass spectrometry measurements. As a result, the need for a thorough investigation of compound-specific isotope fractionation effects introduced by any step of the overall analytical method by standards with known isotopic composition is emphasized. Finally, we address some important points that have to be considered when interpreting data from field investigations.

  12. Amino acid isotopic analysis in agricultural systems

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A relatively new approach to stable isotopic analysis—referred to as compound-specific isotopic analysis (CSIA)—has emerged, centering on the measurement of 15N:14N ratios in amino acids (glutamic acid and phenylalanine). CSIA has recently been used to generate trophic position estimates among anima...

  13. Accurate measurements of transition frequencies and isotope shifts of laser-trapped francium.

    PubMed

    Sanguinetti, S; Calabrese, R; Corradi, L; Dainelli, A; Khanbekyan, A; Mariotti, E; de Mauro, C; Minguzzi, P; Moi, L; Stancari, G; Tomassetti, L; Veronesi, S

    2009-04-01

    An interferometric method is used to improve the accuracy of the 7S-7P transition frequencies of three francium isotopes by 1 order of magnitude. The deduced isotope shifts for 209-211Fr confirm the ISOLDE data. The frequency of the D2 transition of 212Fr--the accepted reference for all Fr isotope shifts--is revised, and a significant difference with the ISOLDE value is found. Our results will be a benchmark for the accuracy of the theory of Fr energy levels, a necessary step to investigate fundamental symmetries. PMID:19340162

  14. Systematic Analysis of Uranium Isotopes

    SciTech Connect

    Young, Phillip G.; Chadwick, Mark B.; MacFarlane, Robert E.; Madland, David G.; Moeller, Peter; Wilson, William B.; Talou, Patrick; Kawano, Toshihiko

    2005-05-24

    We describe recent nuclear model calculations and evaluations of neutron reactions on the uranium isotopes 232-241U in the keV to 30-MeV energy range. This work makes use of extensive sets of measurements for fission, elastic, inelastic (n,xn) and capture, as well as fission probability data. The 235U(n.f) standard cross section was revised, and the fission cross sections of the uranium isotopes, as well as 237Np and 239Pu, were updated using the revised standard. Nuclear reaction model calculations were performed for the whole suite of uranium isotopes to allow us to take advantage of the systematical properties from isotope-to-isotope, which is especially useful for nuclides where few measurements exist. In addition to improving the neutron cross sections and energy-angle distributions, new prompt fission neutron spectra and prompt/delayed neutron multiplicity evaluations are included for several isotopes. These evaluations are among the pre-ENDF/B-VII evaluations that are currently being considered for the new ENDF file. A companion paper in this Conference by MacFarlane describes critical-assembly integral data testing results for U isotopes.

  15. Systematic Analysis of Uranium Isotopes

    NASA Astrophysics Data System (ADS)

    Young, Phillip G.; Chadwick, Mark B.; MacFarlane, Robert E.; Madland, David G.; Möller, Peter; Wilson, William B.; Talou, Patrick; Kawano, Toshihiko

    2005-05-01

    We describe recent nuclear model calculations and evaluations of neutron reactions on the uranium isotopes 232-241U in the keV to 30-MeV energy range. This work makes use of extensive sets of measurements for fission, elastic, inelastic, (n,xn) and capture, as well as fission probability data. The 235U(n.f) standard cross section was revised, and the fission cross sections of the uranium isotopes, as well as 237Np and 239Pu, were updated using the revised standard. Nuclear reaction model calculations were performed for the whole suite of uranium isotopes to allow us to take advantage of the systematical properties from isotope-to-isotope, which is especially useful for nuclides where few measurements exist. In addition to improving the neutron cross sections and energy-angle distributions, new prompt fission neutron spectra and prompt/delayed neutron multiplicity evaluations are included for several isotopes. These evaluations are among the pre-ENDF/B-VII evaluations that are currently being considered for the new ENDF file. A companion paper in this Conference by MacFarlane describes critical-assembly integral data testing results for U isotopes.

  16. Highly accurate isotope composition measurements by a miniature laser ablation mass spectrometer designed for in situ investigations on planetary surfaces

    NASA Astrophysics Data System (ADS)

    Riedo, A.; Meyer, S.; Heredia, B.; Neuland, M. B.; Bieler, A.; Tulej, M.; Leya, I.; Iakovleva, M.; Mezger, K.; Wurz, P.

    2013-10-01

    An experimental procedure for precise and accurate measurements of isotope abundances by a miniature laser ablation mass spectrometer for space research is described. The measurements were conducted on different untreated NIST standards and galena samples by applying pulsed UV laser radiation (266 nm, 3 ns and 20 Hz) for ablation, atomisation, and ionisation of the sample material. Mass spectra of released ions are measured by a reflectron-type time-of-flight mass analyser. A computer controlled performance optimiser was used to operate the system at maximum ion transmission and mass resolution. At optimal experimental conditions, the best relative accuracy and precision achieved for Pb isotope compositions are at the per mill level and were obtained in a range of applied laser irradiances and a defined number of accumulated spectra. A similar relative accuracy and precision was achieved in the study of Pb isotope compositions in terrestrial galena samples. The results for the galena samples are similar to those obtained with a thermal ionisation mass spectrometer (TIMS). The studies of the isotope composition of other elements yielded relative accuracy and precision at the per mill level too, with characteristic instrument parameters for each element. The relative accuracy and precision of the measurements is degrading with lower element/isotope concentration in a sample. For the elements with abundances below 100 ppm these values drop to the percent level. Depending on the isotopic abundances of Pb in minerals, 207Pb/206Pb ages with accuracy in the range of tens of millions of years can be achieved.

  17. Isotope ratio determination in boron analysis.

    PubMed

    Sah, R N; Brown, P H

    1998-01-01

    method of choice for B isotope ratio determination. The current state of instrumental capabilities is adequate for B isotope determination. However, precision and accuracy are primarily limited by sample preparation, introduction, and analytical methodology, including 1. Analyte loss and isotope fractionation during sample preparation. 2. The precision of B isotope determination in small samples, especially those containing low concentrations. 3. Difficult matrices. 4. Memory effects. Sample preparation by alkali fusion allows rapid and complete decomposition of hard-to-digest samples, but high-salt environments of the fused materials require extensive sample purification for B ratio determination. The alternative wet-ashing sample decomposition with HF also results in B loss and isotopic fractionation owing to the high volatility of BF3. Open-vessel dry- or wet-ashing methods usually do not work well for animal samples, and are also prone to B loss and contamination. Closed-vessel microwave digestion overcomes these problems, but the digests of biological materials have high C contents, which cause spectral interference on 11B and affect 11B/10B ratios. Exchange separation/preconcentration of B using exchange (cation or anion exchange, B-specific resin, e.g., Amberlite IRA-743) tend to cause B isotope fractionation, and C eluting from these resin columns may interfere with B isotope ratio determination. Memory effects of B that occur during sample determination may cause serious errors in B isotope ratio determination, especially when samples varying in B concentrations and/or isotope composition are analyzed together. Although the utilization of high-resolution plasma-source MS will undoubtedly improve analytical precision, it is the sample preparation, sample introduction, and analytical methodology that represent the primary limitation to accurate and precise B isotope ratio determination.

  18. Compound specific isotope analysis of organophosphorus pesticides.

    PubMed

    Wu, Langping; Yao, Jun; Trebse, Polonca; Zhang, Ning; Richnow, Hans H

    2014-09-01

    Compound-specific isotope analysis (CSIA) has been established as a tool to study the environmental fate of a wide range of contaminants. In this study, CSIA was developed to analyse the stable carbon isotope signatures of the widely used organophosphorus pesticides: dichlorvos, omethoate and dimethoate. The linearity of the GC-C-IRMS system was tested for target pesticides and led to an acceptable isotope composition within the uncertainty of the instrument. In order to assess the accuracy of the developed method, the effect of the evaporation procedure on measured carbon isotope composition (δ(13)C) values was studied and showed that concentration by evaporation of solvents had no significant isotope effect. The CSIA was then applied to investigate isotope fractionation of the hydrolysis and photolysis of selected pesticides. The carbon isotope fractionation of tested pesticides was quantified by the Rayleigh model, which revealed a bulk enrichment factor (ε) of -0.2±0.1‰ for hydrolysis of dichlorvos, -1.0±0.1‰ and -3.7±1.1‰ for hydrolysis and photolysis of dimethoate respectively. This study is a first step towards the application of CSIA to trace the transport and degradation of organophosphorus pesticides in the environment.

  19. Connecting laboratory behavior to field function through stable isotope analysis.

    PubMed

    Glon, Mael G; Larson, Eric R; Pangle, Kevin L

    2016-01-01

    Inherent difficulties of tracking and observing organisms in the field often leave researchers with no choice but to conduct behavioral experiments under laboratory settings. However, results of laboratory experiments do not always translate accurately to natural conditions. A fundamental challenge in ecology is therefore to scale up from small area and short-duration laboratory experiments to large areas and long durations over which ecological processes generally operate. In this study, we propose that stable isotope analysis may be a tool that can link laboratory behavioral observations to past field interactions or function of individual organisms. We conducted laboratory behavioral assays to measure dominance of invasive rusty crayfish, Orconectes rusticus, and used stable isotope analysis to hindcast trophic positions of these crayfish under preceding natural conditions. We hypothesized that more dominant crayfish in our assays would have higher trophic positions if dominance were related to competitive ability or willingness to pursue high-risk, high-reward prey. We did not find a relationship between crayfish dominance and trophic position, and therefore infer that laboratory dominance of crayfish may not necessarily relate to their ecology in the field. However, this is to our knowledge the first attempt to directly relate laboratory behavior to field performance via stable isotope analysis. We encourage future studies to continue to explore a possible link between laboratory and field behavior via stable isotope analysis, and propose several avenues to do so. PMID:27077010

  20. Connecting laboratory behavior to field function through stable isotope analysis

    PubMed Central

    Larson, Eric R.; Pangle, Kevin L.

    2016-01-01

    Inherent difficulties of tracking and observing organisms in the field often leave researchers with no choice but to conduct behavioral experiments under laboratory settings. However, results of laboratory experiments do not always translate accurately to natural conditions. A fundamental challenge in ecology is therefore to scale up from small area and short-duration laboratory experiments to large areas and long durations over which ecological processes generally operate. In this study, we propose that stable isotope analysis may be a tool that can link laboratory behavioral observations to past field interactions or function of individual organisms. We conducted laboratory behavioral assays to measure dominance of invasive rusty crayfish, Orconectes rusticus, and used stable isotope analysis to hindcast trophic positions of these crayfish under preceding natural conditions. We hypothesized that more dominant crayfish in our assays would have higher trophic positions if dominance were related to competitive ability or willingness to pursue high-risk, high-reward prey. We did not find a relationship between crayfish dominance and trophic position, and therefore infer that laboratory dominance of crayfish may not necessarily relate to their ecology in the field. However, this is to our knowledge the first attempt to directly relate laboratory behavior to field performance via stable isotope analysis. We encourage future studies to continue to explore a possible link between laboratory and field behavior via stable isotope analysis, and propose several avenues to do so. PMID:27077010

  1. Accurate electron affinity of Pb and isotope shifts of binding energies of Pb(.).

    PubMed

    Chen, Xiaolin; Ning, Chuangang

    2016-08-28

    Lead (Pb) was the last element of the group IVA whose electron affinity had a low accuracy around 10 meV before the present work. This was due to the generic threshold photodetachment measurement that cannot extent well below 0.5 eV due to the light source limitation. In the present work, the electron affinity of Pb was determined to be 2877.33(13) cm(-1) or 0.356 743(16) eV for the isotope m = 208. The accuracy was improved by a factor of 500 with respect to the previous laser photodetachment electron spectroscopy. Moreover, remarkable isotope shifts of the binding energy of Pb(-) 6p(3) (4)S3/2 - Pb 6p(2) (3)P2 were observed for m = 206, 207, and 208. PMID:27586918

  2. Accurate electron affinity of Pb and isotope shifts of binding energies of Pb-

    NASA Astrophysics Data System (ADS)

    Chen, Xiaolin; Ning, Chuangang

    2016-08-01

    Lead (Pb) was the last element of the group IVA whose electron affinity had a low accuracy around 10 meV before the present work. This was due to the generic threshold photodetachment measurement that cannot extent well below 0.5 eV due to the light source limitation. In the present work, the electron affinity of Pb was determined to be 2877.33(13) cm-1 or 0.356 743(16) eV for the isotope m = 208. The accuracy was improved by a factor of 500 with respect to the previous laser photodetachment electron spectroscopy. Moreover, remarkable isotope shifts of the binding energy of Pb- 6p3 4S3/2 - Pb 6p2 3P2 were observed for m = 206, 207, and 208.

  3. Ion Mobility Mass Spectrometry Direct Isotope Abundance Analysis

    SciTech Connect

    Manuel J. Manard, Stephan Weeks, Kevin Kyle

    2010-05-27

    The nuclear forensics community is currently engaged in the analysis of illicit nuclear or radioactive material for the purposes of non-proliferations and attribution. One technique commonly employed for gathering nuclear forensics information is isotope analysis. At present, the state-of-the-art methodology for obtaining isotopic distributions is thermal ionization mass spectrometry (TIMS). Although TIMS is highly accurate at determining isotope distributions, the technique requires an elementally pure sample to perform the measurement. The required radiochemical separations give rise to sample preparation times that can be in excess of one to two weeks. Clearly, the nuclear forensics community is in need of instrumentation and methods that can expedite their decision making process in the event of a radiological release or nuclear detonation. Accordingly, we are developing instrumentation that couples a high resolution IM drift cell to the front end of a MS. The IM cell provides a means of separating ions based upon their collision cross-section and mass-to-charge ratio (m/z). Two analytes with the same m/z, but with different collision cross-sections (shapes) would exit the cell at different times, essentially enabling the cell to function in a similar manner to a gas chromatography (GC) column. Thus, molecular and atomic isobaric interferences can be effectively removed from the ion beam. The mobility selected chemical species could then be introduced to a MS for high-resolution mass analysis to generate isotopic distributions of the target analytes. The outcome would be an IM/MS system capable of accurately measuring isotopic distributions while concurrently eliminating isobaric interferences and laboratory radiochemical sample preparation. The overall objective of this project is developing instrumentation and methods to produce near real-time isotope distributions with a modular mass spectrometric system that performs the required gas-phase chemistry and

  4. Accurate hydrogen depth profiling by reflection elastic recoil detection analysis

    SciTech Connect

    Verda, R. D.; Tesmer, Joseph R.; Nastasi, Michael Anthony,; Bower, R. W.

    2001-01-01

    A technique to convert reflection elastic recoil detection analysis spectra to depth profiles, the channel-depth conversion, was introduced by Verda, et al [1]. But the channel-depth conversion does not correct for energy spread, the unwanted broadening in the energy of the spectra, which can lead to errors in depth profiling. A work in progress introduces a technique that corrects for energy spread in elastic recoil detection analysis spectra, the energy spread correction [2]. Together, the energy spread correction and the channel-depth conversion comprise an accurate and convenient hydrogen depth profiling method.

  5. Accurate mass measurements of short-lived isotopes with the MISTRAL* rf spectrometer

    SciTech Connect

    Toader, C.; Audi, G.; Doubre, H.; Jacotin, M.; Henry, S.; Kepinski, J.-F.; Le Scornet, G.; Lunney, D.; Monsanglant, C.; Saint Simon, M. de; Thibault, C.; Borcea, C.; Duma, M.; Lebee, G.

    1999-01-15

    The MISTRAL* experiment has measured its first masses at ISOLDE. Installed in May 1997, this radiofrequency transmission spectrometer is to concentrate on nuclides with particularly short half-lives. MISTRAL received its first stable beam in October and first radioactive beam in November 1997. These first tests, with a plasma ion source, resulted in excellent isobaric separation and reasonable transmission. Further testing and development enabled first data taking in July 1998 on neutron-rich Na isotopes having half-lives as short as 31 ms.

  6. Accurate mass determination of short-lived isotopes by a tandem Penning-trap mass spectrometer

    SciTech Connect

    Stolzenberg, H.; Becker, S.; Bollen, G.; Kern, F.; Kluge, H.; Otto, T.; Savard, G.; Schweikhard, L. ); Audi, G. ); Moore, R.B. ); The ISOLDE Collaboration

    1990-12-17

    A mass spectrometer consisting of two Penning traps has been set up for short-lived isotopes at the on-line mass separator ISOLDE at CERN. The ion beam is collected and cooled in the first trap. After delivery to the second trap, high-accuracy direct mass measurements are made by determining the cyclotron frequency of the stored ions. Measurements have been performed for {sup 118}Cs--{sup 137}Cs. A resolving power of over 10{sup 6} and an accuracy of 1.4{times}10{sup {minus}7} have been achieved, corresponding to about 20 keV.

  7. Fast and accurate procedure for the determination of Cr(VI) in solid samples by isotope dilution mass spectrometry.

    PubMed

    Fabregat-Cabello, Neus; Rodríguez-González, Pablo; Castillo, Ángel; Malherbe, Julien; Roig-Navarro, Antoni F; Long, Stephen E; García Alonso, J Ignacio

    2012-11-20

    We present here a new environmental measurement method for the rapid extraction and accurate quantification of Cr(VI) in solid samples. The quantitative extraction of Cr(VI) is achieved in 10 minutes by means of focused microwave assisted extraction using 50 mmol/L Ethylendiamintetraacetic acid (EDTA) at pH 10 as extractant. In addition, it enables the separation of Cr species by anion exchange chromatography using a mobile phase which is a 1:10 dilution of the extracting solution. Thus, neutralization or acidification steps which are prone to cause interconversion of Cr species are not needed. Another benefit of using EDTA is that it allows to measure Cr(III)-EDTA complex and Cr(VI) simultaneously in an alkaline extraction solution. The application of a 10 minutes focused microwave assisted extraction (5 min at 90 °C plus 5 min at 110 °C) has been shown to quantitatively extract all forms of hexavalent chromium from the standard reference materials (SRM) candidate NIST 2700 and NIST 2701. A double spike isotope dilution mass spectrometry (IDMS) procedure was employed to study chromium interconversion reactions. It was observed that the formation of a Cr(III)-EDTA complex avoided Cr(III) oxidation for these two reference materials. Thus, the use of a double spiking strategy for quantification is not required and a single spike IDMS procedure using isotopically enriched Cr(VI) provided accurate results.

  8. Accurate interlaminar stress recovery from finite element analysis

    NASA Technical Reports Server (NTRS)

    Tessler, Alexander; Riggs, H. Ronald

    1994-01-01

    The accuracy and robustness of a two-dimensional smoothing methodology is examined for the problem of recovering accurate interlaminar shear stress distributions in laminated composite and sandwich plates. The smoothing methodology is based on a variational formulation which combines discrete least-squares and penalty-constraint functionals in a single variational form. The smoothing analysis utilizes optimal strains computed at discrete locations in a finite element analysis. These discrete strain data are smoothed with a smoothing element discretization, producing superior accuracy strains and their first gradients. The approach enables the resulting smooth strain field to be practically C1-continuous throughout the domain of smoothing, exhibiting superconvergent properties of the smoothed quantity. The continuous strain gradients are also obtained directly from the solution. The recovered strain gradients are subsequently employed in the integration o equilibrium equations to obtain accurate interlaminar shear stresses. The problem is a simply-supported rectangular plate under a doubly sinusoidal load. The problem has an exact analytic solution which serves as a measure of goodness of the recovered interlaminar shear stresses. The method has the versatility of being applicable to the analysis of rather general and complex structures built of distinct components and materials, such as found in aircraft design. For these types of structures, the smoothing is achieved with 'patches', each patch covering the domain in which the smoothed quantity is physically continuous.

  9. Device and method for accurately measuring concentrations of airborne transuranic isotopes

    DOEpatents

    McIsaac, C.V.; Killian, E.W.; Grafwallner, E.G.; Kynaston, R.L.; Johnson, L.O.; Randolph, P.D.

    1996-09-03

    An alpha continuous air monitor (CAM) with two silicon alpha detectors and three sample collection filters is described. This alpha CAM design provides continuous sampling and also measures the cumulative transuranic (TRU), i.e., plutonium and americium, activity on the filter, and thus provides a more accurate measurement of airborne TRU concentrations than can be accomplished using a single fixed sample collection filter and a single silicon alpha detector. 7 figs.

  10. Device and method for accurately measuring concentrations of airborne transuranic isotopes

    DOEpatents

    McIsaac, Charles V.; Killian, E. Wayne; Grafwallner, Ervin G.; Kynaston, Ronnie L.; Johnson, Larry O.; Randolph, Peter D.

    1996-01-01

    An alpha continuous air monitor (CAM) with two silicon alpha detectors and three sample collection filters is described. This alpha CAM design provides continuous sampling and also measures the cumulative transuranic (TRU), i.e., plutonium and americium, activity on the filter, and thus provides a more accurate measurement of airborne TRU concentrations than can be accomplished using a single fixed sample collection filter and a single silicon alpha detector.

  11. Isotope Analysis Reveals Foraging Area Dichotomy for Atlantic Leatherback Turtles

    PubMed Central

    Angulo, Elena; Das, Krishna; Girondot, Marc

    2008-01-01

    Background The leatherback turtle (Dermochelys coriacea) has undergone a dramatic decline over the last 25 years, and this is believed to be primarily the result of mortality associated with fisheries bycatch followed by egg and nesting female harvest. Atlantic leatherback turtles undertake long migrations across ocean basins from subtropical and tropical nesting beaches to productive frontal areas. Migration between two nesting seasons can last 2 or 3 years, a time period termed the remigration interval (RI). Recent satellite transmitter data revealed that Atlantic leatherbacks follow two major dispersion patterns after nesting season, through the North Gulf Stream area or more eastward across the North Equatorial Current. However, information on the whole RI is lacking, precluding the accurate identification of feeding areas where conservation measures may need to be applied. Methodology/Principal Findings Using stable isotopes as dietary tracers we determined the characteristics of feeding grounds of leatherback females nesting in French Guiana. During migration, 3-year RI females differed from 2-year RI females in their isotope values, implying differences in their choice of feeding habitats (offshore vs. more coastal) and foraging latitude (North Atlantic vs. West African coasts, respectively). Egg-yolk and blood isotope values are correlated in nesting females, indicating that egg analysis is a useful tool for assessing isotope values in these turtles, including adults when not available. Conclusions/Significance Our results complement previous data on turtle movements during the first year following the nesting season, integrating the diet consumed during the year before nesting. We suggest that the French Guiana leatherback population segregates into two distinct isotopic groupings, and highlight the urgent need to determine the feeding habitats of the turtle in the Atlantic in order to protect this species from incidental take by commercial fisheries. Our

  12. Stable isotope and elemental analysis in ants.

    PubMed

    Smith, Chris R; Tillberg, Chadwick V

    2009-07-01

    Over the past 20 yr, the use of stable isotopes to infer feeding ecology and the examination of how energetic and elemental exchanges are affected by and affect life (ecological stoichiometry) have gained momentum. The ecological diversity of ants makes them interesting models to explore dietary ecology and their role in food webs. Moreover, their ecological dominance in most habitats facilitates sampling. The protocol described here will produce samples adequate for submission to most labs that specialize in high-throughput analysis of stable isotopes; one should check with any particular lab for specific submission instructions. Note, however, that this protocol is designed specifically for the quantification of the natural abundance of stable isotopes; it does not cover the preparation of trace samples. PMID:20147207

  13. A novel automated image analysis method for accurate adipocyte quantification

    PubMed Central

    Osman, Osman S; Selway, Joanne L; Kępczyńska, Małgorzata A; Stocker, Claire J; O’Dowd, Jacqueline F; Cawthorne, Michael A; Arch, Jonathan RS; Jassim, Sabah; Langlands, Kenneth

    2013-01-01

    Increased adipocyte size and number are associated with many of the adverse effects observed in metabolic disease states. While methods to quantify such changes in the adipocyte are of scientific and clinical interest, manual methods to determine adipocyte size are both laborious and intractable to large scale investigations. Moreover, existing computational methods are not fully automated. We, therefore, developed a novel automatic method to provide accurate measurements of the cross-sectional area of adipocytes in histological sections, allowing rapid high-throughput quantification of fat cell size and number. Photomicrographs of H&E-stained paraffin sections of murine gonadal adipose were transformed using standard image processing/analysis algorithms to reduce background and enhance edge-detection. This allowed the isolation of individual adipocytes from which their area could be calculated. Performance was compared with manual measurements made from the same images, in which adipocyte area was calculated from estimates of the major and minor axes of individual adipocytes. Both methods identified an increase in mean adipocyte size in a murine model of obesity, with good concordance, although the calculation used to identify cell area from manual measurements was found to consistently over-estimate cell size. Here we report an accurate method to determine adipocyte area in histological sections that provides a considerable time saving over manual methods. PMID:23991362

  14. Conditional flux analysis and stable isotopes

    NASA Astrophysics Data System (ADS)

    Zeeman, M. J.; Knohl, A.; Sturm, P.; Buchmann, N. C.; Thomas, C. K.

    2009-12-01

    We propose to investigate to what extend conditional flux analysis can benefit from the addition of stable isotope information. Stable isotopes have been recognized for their potential as process tracer, and could add an extra dimension to the conditional flux concept, which aims at directly quantifying component fluxes and identifying their sources. Differences in 13C abundance in carbon dioxide can be used to distinguish assimilation or respiration sources, whereas the 18O abundance expresses differences in water exchange, for instance between canopy and soil. Lending to recent advances in measurement technology, stable isotopes can now be measured at high temporal resolutions (10Hz) required for commonly applied micrometeorological methods such as the eddy-covariance technique, or related conditional flux methods. We will present current ideas on how the conditional flux method, as recently proposed and evaluated by Thomas et al. (2008), Scanlon & Sahu (2008), to perform daytime flux partitioning at the ecosystem level, can be refined by stable isotope analysis (13C and 18O) of carbon dioxide as additional dimension for identification of fluxes.

  15. Isotopic Ratio Outlier Analysis Global Metabolomics of Caenorhabditis elegans

    PubMed Central

    Szewc, Mark A.; Garrett, Timothy; Menger, Robert F.; Yost, Richard A.; Beecher, Chris; Edison, Arthur S.

    2014-01-01

    We demonstrate the global metabolic analysis of Caenorhabditis elegans stress responses using a mass spectrometry-based technique called Isotopic Ratio Outlier Analysis (IROA). In an IROA protocol, control and experimental samples are isotopically labeled with 95% and 5% 13C, and the two sample populations are mixed together for uniform extraction, sample preparation, and LC-MS analysis. This labeling strategy provides several advantages over conventional approaches: 1) compounds arising from biosynthesis are easily distinguished from artifacts, 2) errors from sample extraction and preparation are minimized because the control and experiment are combined into a single sample, 3) measurement of both the molecular weight and the exact number of carbon atoms in each molecule provides extremely accurate molecular formulae, and 4) relative concentrations of all metabolites are easily determined. A heat shock perturbation was conducted on C. elegans to demonstrate this approach. We identified many compounds that significantly changed upon heat shock, including several from the purine metabolism pathway, which we use to demonstrate the approach. The metabolomic response information by IROA may be interpreted in the context of a wealth of genetic and proteomic information available for C. elegans. Furthermore, the IROA protocol can be applied to any organism that can be isotopically labeled, making it a powerful new tool in a global metabolomics pipeline. PMID:24274725

  16. Precise and accurate measurement of U and Th isotopes via ICP-MS using a single solution

    NASA Astrophysics Data System (ADS)

    Mertz-Kraus, R.; Sharp, W. D.; Ludwig, K. R.

    2012-04-01

    U-series isotope measurements by ICP-MS commonly utilize separate runs for U and Th and standard-sample bracketing to determine correction factors for mass fractionation and ion counter yields. Here we present an approach where all information necessary to calculate an age (aside from background/baseline levels) is determined while analyzing a single solution containing both U and Th. This internally calibrated procedure should reduce any bias caused by distinct behavior of sample versus standard solutions during analysis and offers advantages including simplicity of operation, calculation of preliminary ages in real time, and simplified analysis of errors and their sources. Hellstrom (2003) developed a single-solution, internally-calibrated technique for an ICP-MS with multiple ion counters, but to our knowledge no such technique is available for an ICP-MS with a single ion counter. We use a Thermo Neptune Plus multi-collector ICP-MS with eight movable Faraday cups and a fixed center cup/ion counter equipped with a high abundance-sensitivity filter (RPQ). We use Faraday cups to measure all masses except 230 and 234, which are measured on the ion counter with the RPQ detuned (i.e., Suppressor voltage = 9950 V). 238U is maintained in a cup throughout the analysis to avoid reflections and is used to normalize signal instabilities related to sample introduction. Each analysis has a three-part structure, i.e. 1) background/baseline levels, 2) sample composition, and 3) peak-tails are sequentially determined. In step 1, multiplier dark noise/Faraday baselines plus background intensities at each mass are determined while aspirating running solution. During sample measurement in step 2, ion counter yields for Th and U are determined using signals of 300-400 kcps for 229Th and 233U by measuring 229Th/238U and 233U/238U ratios first with the minor masses on the ion counter and then with both masses in cups. Mass bias can be determined using the 233U/236U ratio of the spike

  17. Highly accurate quantification of hydroxyproline-containing peptides in blood using a protease digest of stable isotope-labeled collagen.

    PubMed

    Taga, Yuki; Kusubata, Masashi; Ogawa-Goto, Kiyoko; Hattori, Shunji

    2014-12-17

    Collagen-derived hydroxyproline (Hyp)-containing dipeptides and tripeptides, which are known to possess physiological functions, appear in blood at high concentrations after oral ingestion of gelatin hydrolysate. However, highly accurate and sensitive quantification of the Hyp-containing peptides in blood has been challenging because of the analytical interference from numerous other blood components. We recently developed a stable isotope-labeled collagen named "SI-collagen" that can be used as an internal standard in various types of collagen analyses employing liquid chromatography-mass spectrometry (LC-MS). Here we prepared stable isotope-labeled Hyp-containing peptides from SI-collagen using trypsin/chymotrypsin and plasma proteases by mimicking the protein degradation pathways in the body. With the protease digest of SI-collagen used as an internal standard mixture, we achieved highly accurate simultaneous quantification of Hyp and 13 Hyp-containing peptides in human blood by LC-MS. The area under the plasma concentration-time curve of Hyp-containing peptides ranged from 0.663 ± 0.022 nmol/mL·h for Pro-Hyp-Gly to 163 ± 1 nmol/mL·h for Pro-Hyp after oral ingestion of 25 g of fish gelatin hydrolysate, and the coefficient of variation of three separate measurements was <7% for each peptide except for Glu-Hyp-Gly, which was near the detection limit. Our method is useful for absorption/metabolism studies of the Hyp-containing peptides and development of functionally characterized gelatin hydrolysate.

  18. Compound-specific isotope analysis of benzotriazole and its derivatives.

    PubMed

    Spahr, Stephanie; Huntscha, Sebastian; Bolotin, Jakov; Maier, Michael P; Elsner, Martin; Hollender, Juliane; Hofstetter, Thomas B

    2013-03-01

    Compound-specific isotope analysis (CSIA) is an important tool for the identification of contaminant sources and transformation pathways, but it is rarely applied to emerging aquatic micropollutants owing to a series of instrumental challenges. Using four different benzotriazole corrosion inhibitors and its derivatives as examples, we obtained evidence that formation of organometallic complexes of benzotriazoles with parts of the instrumentation impedes isotope analysis. Therefore, we propose two strategies for accurate [Formula: see text]C and [Formula: see text]N measurements of polar organic micropollutants by gas chromatography isotope ratio mass spectrometry (GC/IRMS). Our first approach avoids metallic components and uses a Ni/Pt reactor for benzotriazole combustion while the second is based on the coupling of online methylation to the established GC/IRMS setup. Method detection limits for on-column injection of benzotriazole, as well as its 1-CH[Formula: see text]-, 4-CH[Formula: see text]-, and 5-CH[Formula: see text]-substituted species were 0.1-0.3 mM and 0.1-1.0 mM for δ(13)C and δ(15)N analysis respectively, corresponding to injected masses of 0.7-1.8 nmol C and 0.4-3.0 nmol N, respectively. The Ni/Pt reactor showed good precision and was very long-lived ([Formula: see text]1000 successful measurements). Coupling isotopic analysis to offline solid-phase extraction enabled benzotriazole-CSIA in tap water, wastewater treatment effluent, activated sludge, and in commercial dishwashing products. A comparison of [Formula: see text]C and [Formula: see text]N values from different benzotriazoles and benzotriazole derivatives, both from commercial standards and in dishwashing detergents, reveals the potential application of the proposed method for source apportionment. PMID:23224662

  19. Electron Microprobe Analysis Techniques for Accurate Measurements of Apatite

    NASA Astrophysics Data System (ADS)

    Goldoff, B. A.; Webster, J. D.; Harlov, D. E.

    2010-12-01

    Apatite [Ca5(PO4)3(F, Cl, OH)] is a ubiquitous accessory mineral in igneous, metamorphic, and sedimentary rocks. The mineral contains halogens and hydroxyl ions, which can provide important constraints on fugacities of volatile components in fluids and other phases in igneous and metamorphic environments in which apatite has equilibrated. Accurate measurements of these components in apatite are therefore necessary. Analyzing apatite by electron microprobe (EMPA), which is a commonly used geochemical analytical technique, has often been found to be problematic and previous studies have identified sources of error. For example, Stormer et al. (1993) demonstrated that the orientation of an apatite grain relative to the incident electron beam could significantly affect the concentration results. In this study, a variety of alternative EMPA operating conditions for apatite analysis were investigated: a range of electron beam settings, count times, crystal grain orientations, and calibration standards were tested. Twenty synthetic anhydrous apatite samples that span the fluorapatite-chlorapatite solid solution series, and whose halogen concentrations were determined by wet chemistry, were analyzed. Accurate measurements of these samples were obtained with many EMPA techniques. One effective method includes setting a static electron beam to 10-15nA, 15kV, and 10 microns in diameter. Additionally, the apatite sample is oriented with the crystal’s c-axis parallel to the slide surface and the count times are moderate. Importantly, the F and Cl EMPA concentrations are in extremely good agreement with the wet-chemical data. We also present EMPA operating conditions and techniques that are problematic and should be avoided. J.C. Stormer, Jr. et al., Am. Mineral. 78 (1993) 641-648.

  20. Existing and emerging technologies for measuring stable isotope labelled retinol in biological samples: isotope dilution analysis of body retinol stores.

    PubMed

    Preston, Tom

    2014-01-01

    This paper discusses some of the recent improvements in instrumentation used for stable isotope tracer measurements in the context of measuring retinol stores, in vivo. Tracer costs, together with concerns that larger tracer doses may perturb the parameter under study, demand that ever more sensitive mass spectrometric techniques are developed. GCMS is the most widely used technique. It has high sensitivity in terms of sample amount and uses high resolution GC, yet its ability to detect low isotope ratios is limited by background noise. LCMSMS may become more accessible for tracer studies. Its ability to measure low level stable isotope tracers may prove superior to GCMS, but it is isotope ratio MS (IRMS) that has been designed specifically for low level stable isotope analysis through accurate analysis of tracer:tracee ratios (the tracee being the unlabelled species). Compound-specific isotope analysis, where GC is interfaced to IRMS, is gaining popularity. Here, individual 13C-labelled compounds are separated by GC, combusted to CO2 and transferred on-line for ratiometric analysis by IRMS at the ppm level. However, commercially-available 13C-labelled retinol tracers are 2 - 4 times more expensive than deuterated tracers. For 2H-labelled compounds, GC-pyrolysis-IRMS has now become more generally available as an operating mode on the same IRMS instrument. Here, individual compounds are separated by GC and pyrolysed to H2 at high temperature for analysis by IRMS. It is predicted that GC-pyrolysis-IRMS will facilitate low level tracer procedures to measure body retinol stores, as has been accomplished in the case of fatty acids and amino acids. Sample size requirements for GC-P-IRMS may exceed those of GCMS, but this paper discusses sample preparation procedures and predicts improvements, particularly in the efficiency of sample introduction.

  1. pH-dependent equilibrium isotope fractionation associated with the compound specific nitrogen and carbon isotope analysis of substituted anilines by SPME-GC/IRMS.

    PubMed

    Skarpeli-Liati, Marita; Turgeon, Aurora; Garr, Ashley N; Arnold, William A; Cramer, Christopher J; Hofstetter, Thomas B

    2011-03-01

    Solid-phase microextraction (SPME) coupled to gas chromatography/isotope ratio mass spectrometry (GC/IRMS) was used to elucidate the effects of N-atom protonation on the analysis of N and C isotope signatures of selected aromatic amines. Precise and accurate isotope ratios were measured using polydimethylsiloxane/divinylbenzene (PDMS/DVB) as the SPME fiber material at solution pH-values that exceeded the pK(a) of the substituted aniline's conjugate acid by two pH-units. Deviations of δ(15)N and δ(13)C-values from reference measurements by elemental analyzer IRMS were small (<0.9‰) and within the typical uncertainties of isotope ratio measurements by SPME-GC/IRMS. Under these conditions, the detection limits for accurate isotope ratio measurements were between 0.64 and 2.1 mg L(-1) for δ(15)N and between 0.13 and 0.54 mg L(-1) for δ(13)C, respectively. Substantial inverse N isotope fractionation was observed by SPME-GC/IRMS as the fraction of protonated species increased with decreasing pH leading to deviations of -20‰ while the corresponding δ(13)C-values were largely invariant. From isotope ratio analysis at different solution pHs and theoretical calculations by density functional theory, we derived equilibrium isotope effects, EIEs, pertinent to aromatic amine protonation of 0.980 and 1.001 for N and C, respectively, which were very similar for all compounds investigated. Our work shows that N-atom protonation can compromise accurate compound-specific N isotope analysis of aromatic amines.

  2. Accurate first-principles calculations for 12CH3D infrared spectra from isotopic and symmetry transformations.

    PubMed

    Rey, Michaël; Nikitin, Andrei V; Tyuterev, Vladimir G

    2014-07-28

    Accurate variational high-resolution spectra calculations in the range 0-8000 cm(-1) are reported for the first time for the monodeutered methane ((12)CH3D). Global calculations were performed by using recent ab initio surfaces for line positions and line intensities derived from the main isotopologue (12)CH4. Calculation of excited vibrational levels and high-J rovibrational states is described by using the normal mode Eckart-Watson Hamiltonian combined with irreducible tensor formalism and appropriate numerical procedures for solving the quantum nuclear motion problem. The isotopic H→D substitution is studied in details by means of symmetry and nonlinear normal mode coordinate transformations. Theoretical spectra predictions are given up to J = 25 and compared with the HITRAN 2012 database representing a compilation of line lists derived from analyses of experimental spectra. The results are in very good agreement with available empirical data suggesting that a large number of yet unassigned lines in observed spectra could be identified and modeled using the present approach. PMID:25084919

  3. The Separation and Isotopic Analysis Seawater Cu and Zn

    NASA Astrophysics Data System (ADS)

    Bermin, J.; Vance, D.; Archer, C.; Statham, P. J.

    2004-12-01

    Many transition metals are key micronutrients and their concentration profiles in the oceans often show nutrient-like patterns, with strong surface depletions and deep enrichments1. In addition, their biological usage has been shown to induce isotopic fractionations2 so that the precise and accurate analysis of their isotope systems in seawater has potential applications in tracing metal micronutrient usage in the past ocean. The analytical challenges involved in realising this goal are, however, considerable, given the low concentrations of transition metals in seawater and the requirement to extract small amounts from large samples at low blank and with no artificial isotopic fractionation. Here we present a method for the separation an analysis of Cu and Zn isotopes that is applicable to 0.1-5 L samples of seawater. Trace metals were concentrated from seawater using a Chelex-100 ion-exchange column3 and further purified and separated from each other using a small anion column4,5. All isotopic analyses were performed on a ThermoFinnigan Neptune instrument at the University of Bristol. The main requirements for precise and accurate isotopic analyses are a low contribution from analytical blank and the robust correction for analytical mass discrimination. Our blanks allow the analysis of seawater samples of 50-250 mL for Cu, samples of about 100 mL for Zn in the deep oceans and for Zn-depleted open ocean surface water samples of around 5L. The correction for mass discrimination is most readily considered as two components - that occurring during the chemical separation procedure in response to non-100% yields and that occurring in the mass spectrometer. Correction of all mass discrimination throughout the procedure is most robustly done for Zn and Fe using a double-spike that is added prior to any chemical treatment. This approach has been tested using standard-doped seawater samples that had previously been stripped of their metal contents using the Chelex column

  4. Cyberinfrastructure for isotope analysis and modeling

    NASA Astrophysics Data System (ADS)

    Bowen, Gabriel J.; West, Jason B.; Zhao, Lan; Takahashi, George; Miller, Chris; Zhang, Tonglin

    2012-05-01

    As the quantity and complexity of scientific data expand, accessible interfaces for data manipulation and analysis are needed to support broad and efficient data use. The Isoscapes Modeling, Analysis, and Prediction (IsoMAP; http://isomap.org) Web-based geographical information system (GIS) gateway is an example of such a resource. Recently launched with support from the U.S. National Science Foundation (NSF) Division of Biological Infrastructure, IsoMAP enables analysis and integration of diverse light stable isotope and environmental data by a broad-based user community. It provides an intuitive, spatial interface that streamlines data analysis, modeling, and exploration in research ranging from greenhouse gas biogeochemistry to food science.

  5. Measurement of isotope abundance variations in nature by gravimetric spiking isotope dilution analysis (GS-IDA).

    PubMed

    Chew, Gina; Walczyk, Thomas

    2013-04-01

    Subtle variations in the isotopic composition of elements carry unique information about physical and chemical processes in nature and are now exploited widely in diverse areas of research. Reliable measurement of natural isotope abundance variations is among the biggest challenges in inorganic mass spectrometry as they are highly sensitive to methodological bias. For decades, double spiking of the sample with a mix of two stable isotopes has been considered the reference technique for measuring such variations both by multicollector-inductively coupled plasma mass spectrometry (MC-ICPMS) and multicollector-thermal ionization mass spectrometry (MC-TIMS). However, this technique can only be applied to elements having at least four stable isotopes. Here we present a novel approach that requires measurement of three isotope signals only and which is more robust than the conventional double spiking technique. This became possible by gravimetric mixing of the sample with an isotopic spike in different proportions and by applying principles of isotope dilution for data analysis (GS-IDA). The potential and principle use of the technique is demonstrated for Mg in human urine using MC-TIMS for isotopic analysis. Mg is an element inaccessible to double spiking methods as it consists of three stable isotopes only and shows great potential for metabolically induced isotope effects waiting to be explored.

  6. Progress toward accurate high spatial resolution actinide analysis by EPMA

    NASA Astrophysics Data System (ADS)

    Jercinovic, M. J.; Allaz, J. M.; Williams, M. L.

    2010-12-01

    High precision, high spatial resolution EPMA of actinides is a significant issue for geochronology, resource geochemistry, and studies involving the nuclear fuel cycle. Particular interest focuses on understanding of the behavior of Th and U in the growth and breakdown reactions relevant to actinide-bearing phases (monazite, zircon, thorite, allanite, etc.), and geochemical fractionation processes involving Th and U in fluid interactions. Unfortunately, the measurement of minor and trace concentrations of U in the presence of major concentrations of Th and/or REEs is particularly problematic, especially in complexly zoned phases with large compositional variation on the micro or nanoscale - spatial resolutions now accessible with modern instruments. Sub-micron, high precision compositional analysis of minor components is feasible in very high Z phases where scattering is limited at lower kV (15kV or less) and where the beam diameter can be kept below 400nm at high current (e.g. 200-500nA). High collection efficiency spectrometers and high performance electron optics in EPMA now allow the use of lower overvoltage through an exceptional range in beam current, facilitating higher spatial resolution quantitative analysis. The U LIII edge at 17.2 kV precludes L-series analysis at low kV (high spatial resolution), requiring careful measurements of the actinide M series. Also, U-La detection (wavelength = 0.9A) requires the use of LiF (220) or (420), not generally available on most instruments. Strong peak overlaps of Th on U make highly accurate interference correction mandatory, with problems compounded by the ThMIV and ThMV absorption edges affecting peak, background, and interference calibration measurements (especially the interference of the Th M line family on UMb). Complex REE bearing phases such as monazite, zircon, and allanite have particularly complex interference issues due to multiple peak and background overlaps from elements present in the activation

  7. Plutonium Isotopic Gamma-Ray Analysis

    1992-01-08

    The MGA8 (Multiple Group Analysis) program determines the relative abundances of plutonium and other actinide isotopes in different materials. The program analyzes spectra taken of such samples using a 4096-channel germanium (Ge) gamma-ray spectrometer. The code can be run in a one or two detector mode. The first spectrum, which is required and must be taken at a gain of 0.075 Kev/channel with a high resolution planar detector, contains the 0-300 Kev energy region. Themore » second spectrum, which is optional, must be taken at a gain of 0.25 Kev/channel; it becomes important when analyzing high burnup samples (concentration of Pu241 greater than one percent). Isotopic analysis precisions of one percent or better can be obtained, and no calibrations are required. The system also measures the abundances of U235, U238, Np237, and Am241. A special calibration option is available to perform a one-time peak-shape characterization when first using a new detector system.« less

  8. Carbon-isotopic analysis of dissolved acetate

    NASA Technical Reports Server (NTRS)

    Gelwicks, J. T.; Hayes, J. M.

    1990-01-01

    Heating of dried, acetate-containing solids together with oxalic acid dihydrate conveniently releases acetic acid for purification by gas chromatography. For determination of the carbon-isotopic composition of total acetate, the acetate-containing zone of the chromatographic effluent can be routed directly to a combustion furnace coupled to a vacuum system allowing recovery, purification, and packaging of CO2 for mass-spectrometric analysis. For analysis of methyl carbon, acetic acid can be cryogenically trapped from the chromatographic effluent, then transferred to a tube containing excess NaOH. The tube is evacuated, sealed, and heated to 500 degrees C to produce methane by pyrolysis of sodium acetate. Subsequent combustion of the methane allows determination of the 13C content at the methyl position in the parent acetate. With typical blanks, the standard deviation of single analyses is less than 0.4% for acetate samples larger than 5 micromoles. A full treatment of uncertainties is outlined.

  9. Compound specific stable isotope analysis vs. bulk stable isotope analysis of agricultural food products

    NASA Astrophysics Data System (ADS)

    Psomiadis, David; Horváth, Balázs; Nehlich, Olaf; Bodiselitsch, Bernd

    2015-04-01

    The bulk analysis of stable isotopes (carbon, nitrogen, sulphur, oxygen and hydrogen) from food staples is a common tool for inferring origin and/or fraud of food products. Many studies have shown that bulk isotope analyses of agricultural products are able to separate large geographical areas of food origin. However, in micro-localities (regions, districts, and small ranges) these general applications fail in precision and discriminative power. The application of compound specific analysis of specific components of food products helps to increase the precision of established models. Compound groups like fatty acids (FAMEs), vitamins or amino acids can help to add further detailed information on physiological pathways and local conditions (micro-climate, soil, water availability) and therefore might add further information for the separation of micro-localities. In this study we are aiming to demonstrate the power and surplus of information of compound specific isotope analysis in comparison to bulk analysis of agricultural products (e.g. olive oil, cereal crops or similar products) and discuss the advantages and disadvantages of such (labor intense) analysis methods. Here we want to identify tools for further detailed analysis of specific compounds with high powers of region separation for better prediction models.

  10. Estimating pathway-specific contributions to biodegradation in aquifers based on dual isotope analysis: theoretical analysis and reactive transport simulations.

    PubMed

    Centler, Florian; Heße, Falk; Thullner, Martin

    2013-09-01

    At field sites with varying redox conditions, different redox-specific microbial degradation pathways contribute to total contaminant degradation. The identification of pathway-specific contributions to total contaminant removal is of high practical relevance, yet difficult to achieve with current methods. Current stable-isotope-fractionation-based techniques focus on the identification of dominant biodegradation pathways under constant environmental conditions. We present an approach based on dual stable isotope data to estimate the individual contributions of two redox-specific pathways. We apply this approach to carbon and hydrogen isotope data obtained from reactive transport simulations of an organic contaminant plume in a two-dimensional aquifer cross section to test the applicability of the method. To take aspects typically encountered at field sites into account, additional simulations addressed the effects of transverse mixing, diffusion-induced stable-isotope fractionation, heterogeneities in the flow field, and mixing in sampling wells on isotope-based estimates for aerobic and anaerobic pathway contributions to total contaminant biodegradation. Results confirm the general applicability of the presented estimation method which is most accurate along the plume core and less accurate towards the fringe where flow paths receive contaminant mass and associated isotope signatures from the core by transverse dispersion. The presented method complements the stable-isotope-fractionation-based analysis toolbox. At field sites with varying redox conditions, it provides a means to identify the relative importance of individual, redox-specific degradation pathways.

  11. Accurate measurement of bromine contents in plastic samples by instrumental neutron activation analysis.

    PubMed

    Kim, I J; Lee, K S; Hwang, E; Min, H S; Yim, Y H

    2013-03-26

    Accurate measurements of bromine contents in plastic samples were made by the direct comparator instrumental neutron activation analysis (INAA). Individual factors affecting the measurements were comprehensively evaluated and compensated, including the volatility loss of bromine from standard comparators, the background bromine level in the filter papers used for preparation of the standard comparators, nuclear interference, γ-ray spectral interference and the variance among replicates of the samples. Uncertainty contributions from those factors were thoroughly evaluated and included in the uncertainty budgeting of the INAA measurement. (81)Br was chosen as the target isotope, and the INAA measurements for bromine were experimentally confirmed to exhibit good linearity within a bromine content range of 10-170 μg. The established method has been applied to the analysis of eight plastic samples: four commercially available certified reference materials (CRMs) of polyethylene and polystyrene and four acrylonitrile butadiene styrene (ABS) samples prepared as the candidate reference materials (KRISS CRM 113-01-012, -013, -014 and -015). The bromine contents of the samples were calculated at three different γ-ray energies and compared, showing good agreement. The results of the four CRMs also showed good consistency with their certified values within the stated uncertainties. Finally, the bromine contents of the ABS samples were determined with expanded uncertainties (at a 95% level of confidence) between 2.5% and 5% in a bromine content range of 25-900 mg kg(-1).

  12. Accurate measurement of bromine contents in plastic samples by instrumental neutron activation analysis.

    PubMed

    Kim, I J; Lee, K S; Hwang, E; Min, H S; Yim, Y H

    2013-03-26

    Accurate measurements of bromine contents in plastic samples were made by the direct comparator instrumental neutron activation analysis (INAA). Individual factors affecting the measurements were comprehensively evaluated and compensated, including the volatility loss of bromine from standard comparators, the background bromine level in the filter papers used for preparation of the standard comparators, nuclear interference, γ-ray spectral interference and the variance among replicates of the samples. Uncertainty contributions from those factors were thoroughly evaluated and included in the uncertainty budgeting of the INAA measurement. (81)Br was chosen as the target isotope, and the INAA measurements for bromine were experimentally confirmed to exhibit good linearity within a bromine content range of 10-170 μg. The established method has been applied to the analysis of eight plastic samples: four commercially available certified reference materials (CRMs) of polyethylene and polystyrene and four acrylonitrile butadiene styrene (ABS) samples prepared as the candidate reference materials (KRISS CRM 113-01-012, -013, -014 and -015). The bromine contents of the samples were calculated at three different γ-ray energies and compared, showing good agreement. The results of the four CRMs also showed good consistency with their certified values within the stated uncertainties. Finally, the bromine contents of the ABS samples were determined with expanded uncertainties (at a 95% level of confidence) between 2.5% and 5% in a bromine content range of 25-900 mg kg(-1). PMID:23498117

  13. An optimized method for the accurate determination of patulin in apple products by isotope dilution-liquid chromatography/mass spectrometry.

    PubMed

    Seo, Miyeong; Kim, Byungjoo; Baek, Song-Yee

    2015-07-01

    Patulin, a mycotoxin produced by several molds in fruits, has been frequently detected in apple products. Therefore, regulatory bodies have established recommended maximum permitted patulin concentrations for each type of apple product. Although several analytical methods have been adopted to determine patulin in food, quality control of patulin analysis is not easy, as reliable certified reference materials (CRMs) are not available. In this study, as a part of a project for developing CRMs for patulin analysis, we developed isotope dilution liquid chromatography-tandem mass spectrometry (ID-LC/MS/MS) as a higher-order reference method for the accurate value-assignment of CRMs. (13)C7-patulin was used as internal standard. Samples were extracted with ethyl acetate to improve recovery. For further sample cleanup with solid-phase extraction (SPE), the HLB SPE cartridge was chosen after comparing with several other types of SPE cartridges. High-performance liquid chromatography was performed on a multimode column for proper retention and separation of highly polar and water-soluble patulin from sample interferences. Sample extracts were analyzed by LC/MS/MS with electrospray ionization in negative ion mode with selected reaction monitoring of patulin and (13)C7-patulin at m/z 153→m/z 109 and m/z 160→m/z 115, respectively. The validity of the method was tested by measuring gravimetrically fortified samples of various apple products. In addition, the repeatability and the reproducibility of the method were tested to evaluate the performance of the method. The method was shown to provide accurate measurements in the 3-40 μg/kg range with a relative expanded uncertainty of around 1%.

  14. Preparative separation of underivatized amino acids for compound-specific stable isotope analysis and radiocarbon dating of hydrolyzed bone collagen.

    PubMed

    Tripp, Jennifer A; McCullagh, James S O; Hedges, Robert E M

    2006-01-01

    Analysis of stable and radioactive isotopes from bone collagen provides useful information to archaeologists about the origin and age of bone artifacts. Isolation and analysis of single amino acids from the proteins can provide additional and more accurate information by removing contamination and separating a bulk isotope signal into its constituent parts. In this paper, we report a new method for the separation and isolation of underivatized amino acids from bone collagen, and their analysis by isotope ratio MS and accelerator MS. RP chromatography is used to separate the amino acids with nonpolar side chains, followed by an ion pair separation to isolate the remaining amino acids. The method produces single amino acids with little or no contamination from the separation process and allows for the measurement of accurate stable isotope ratios and pure samples for radiocarbon dating.

  15. System and method for high precision isotope ratio destructive analysis

    SciTech Connect

    Bushaw, Bruce A; Anheier, Norman C; Phillips, Jon R

    2013-07-02

    A system and process are disclosed that provide high accuracy and high precision destructive analysis measurements for isotope ratio determination of relative isotope abundance distributions in liquids, solids, and particulate samples. The invention utilizes a collinear probe beam to interrogate a laser ablated plume. This invention provides enhanced single-shot detection sensitivity approaching the femtogram range, and isotope ratios that can be determined at approximately 1% or better precision and accuracy (relative standard deviation).

  16. Accurate experimental determination of the isotope effects on the triple point temperature of water. I. Dependence on the 2H abundance

    NASA Astrophysics Data System (ADS)

    Faghihi, V.; Peruzzi, A.; Aerts-Bijma, A. T.; Jansen, H. G.; Spriensma, J. J.; van Geel, J.; Meijer, H. A. J.

    2015-12-01

    Variation in the isotopic composition of water is one of the major contributors to uncertainty in the realization of the triple point of water (TPW). Although the dependence of the TPW on the isotopic composition of the water has been known for years, there is still a lack of a detailed and accurate experimental determination of the values for the correction constants. This paper is the first of two articles (Part I and Part II) that address quantification of isotope abundance effects on the triple point temperature of water. In this paper, we describe our experimental assessment of the 2H isotope effect. We manufactured five triple point cells with prepared water mixtures with a range of 2H isotopic abundances encompassing widely the natural abundance range, while the 18O and 17O isotopic abundance were kept approximately constant and the 18O  -  17O ratio was close to the Meijer-Li relationship for natural waters. The selected range of 2H isotopic abundances led to cells that realised TPW temperatures between approximately  -140 μK to  +2500 μK with respect to the TPW temperature as realized by VSMOW (Vienna Standard Mean Ocean Water). Our experiment led to determination of the value for the δ2H correction parameter of A2H  =  673 μK / (‰ deviation of δ2H from VSMOW) with a combined uncertainty of 4 μK (k  =  1, or 1σ).

  17. Chemical preparation of an isotopically enriched superoxide dismutase and its characterization as a standard for species-specific isotope dilution analysis.

    PubMed

    Deitrich, Christian L; Raab, Andrea; Pioselli, Barbara; Thomas-Oates, Jane E; Feldmann, Jörg

    2007-11-01

    The development of methods to analyze accurately and precisely individual metalloproteins is of increasing importance. Here we describe for the first time the chemical preparation and characterization of an isotopically enriched metalloenzyme containing two different metal isotopes. Its evaluation as a standard in species-specific isotope dilution analysis by HPLC coupled to inductively coupled plasma mass spectrometry is carefully evaluated. Our model enzyme bovine superoxide dismutase (SOD) contains both Cu and Zn and is remarkably stable at high temperatures and even under denaturing conditions. The enzyme's metal cofactors were removed under a range of different conditions and replaced with isotopically enriched 65Cu and 68Zn. Depending on the conditions, various isotopic ratios differing from the natural Cu and Zn abundances were obtained for the reconstituted enzyme. Both the wild type and isotopically enriched enzyme had the same migration pattern on native 1D-PAGE. Using an enzyme activity test, we showed that the incorporated 65Cu was bound to the right SOD-binding site, since the measured activity correlated directly with the amount of Cu incorporated. Mixing the native and the isotopically enriched enzyme standard with free enriched 65Cu and 68Zn or a metal chelator did not result in any exchange or loss of the metals from the enzyme at neutral pH. This verifies the stability of the enzyme metal center under the chosen conditions. The isotopically enriched enzyme standard was spiked into a wild type SOD solution to evaluate its use for species-specific isotope dilution experiments. To our knowledge, this is the first report of the chemical preparation of a metalloenzyme containing two different isotopically enriched metals. We provide evidence that the incorporated isotopically enriched metals are bound to the right binding site of SOD using an specific enzymatic activity assay.

  18. Radionuclide Data Analysis and Evaluation: More Information From Fewer Isotopes

    NASA Astrophysics Data System (ADS)

    Prinke, A.; McIntyre, J.; Cooper, M.; Haas, D.; Lowrey, J.; Miley, H.; Schrom, B.; Suckow, T.

    2013-12-01

    The analysis of the International Monitoring System radionuclide data sets provides daily concentrations for both particulate and radioxenon isotopes. These isotopes can come from many potential sources such as nuclear reactors, nuclear physics experiments, and medical isotope production. These interesting but irrelevant sources have several of the same radio-isotopic signatures from above or underground nuclear explosions and must be ruled out as part of the determination that an event originated as a nuclear explosion. There are several methods under development that aid in this determination and this poster will briefly cover each: radio-isotopic ratios and parent daughter relationships, co-detection of radioxenon and isotopes found on particulates, and past detection history.

  19. Accurate Quantification of Selenoprotein P (SEPP1) in Plasma Using Isotopically Enriched Seleno-peptides and Species-Specific Isotope Dilution with HPLC Coupled to ICP-MS/MS.

    PubMed

    Deitrich, Christian L; Cuello-Nuñez, Susana; Kmiotek, Diana; Torma, Frank Attila; Del Castillo Busto, Maria Estela; Fisicaro, Paola; Goenaga-Infante, Heidi

    2016-06-21

    A novel strategy for the absolute quantification of selenium (Se) included in selenoprotein P (SEPP1), an important biomarker for human nutrition and disease, including diabetes and cancer, is presented here for the first time. It is based on the use of species-specific double isotope dilution mass spectrometry (SSIDA) in combination with HPLC-ICP-MS/MS for the determination of protein bound Se down to the peptide level in a complex plasma matrix with a total content of Se of 105.5 μg kg(-1). The method enabled the selective Se speciation analysis of human plasma samples without the need of extensive cleanup or preconcentration steps as required for traditional protein mass spectrometric approaches. To assess the method accuracy, two plasma reference materials, namely, BCR-637 and SRM1950, for which literature data and a reference value for SEPP1 have been reported, were analyzed using complementary hyphenated methods and the species-specific approach developed in this work. The Se mass fractions obtained via the isotopic ratios (78)Se/(76)Se and (82)Se/(76)Se for each of the Se-peptides, namely, ENLPSLCSUQGLR (ENL) and AEENITESCQUR (AEE) (where U is SeCys), were found to agree within 2.4%. A relative expanded combined uncertainty (k = 2) of 5.4% was achieved for a Se (as SEPP1) mass fraction of approximately 60 μg kg(-1). This work represents a systematic approach to the accurate quantitation of plasma SEPP1 at clinical levels using SSIDA quantification. Such methodology will be invaluable for the certification of reference materials and the provision of reference values to clinical measurements and clinical trials. PMID:27108743

  20. Improvements in Accurate GPS Positioning Using Time Series Analysis

    NASA Astrophysics Data System (ADS)

    Koyama, Yuichiro; Tanaka, Toshiyuki

    Although the Global Positioning System (GPS) is used widely in car navigation systems, cell phones, surveying, and other areas, several issues still exist. We focus on the continuous data received in public use of GPS, and propose a new positioning algorithm that uses time series analysis. By fitting an autoregressive model to the time series model of the pseudorange, we propose an appropriate state-space model. We apply the Kalman filter to the state-space model and use the pseudorange estimated by the filter in our positioning calculations. The results of the authors' positioning experiment show that the accuracy of the proposed method is much better than that of the standard method. In addition, as we can obtain valid values estimated by time series analysis using the state-space model, the proposed state-space model can be applied to several other fields.

  1. Use of stable isotope analysis in determining aquatic food webs

    EPA Science Inventory

    Stable isotope analysis is a useful tool for describing resource-consumer dynamics in ecosystems. In general, organisms of a given trophic level or functional feeding group will have a stable isotope ratio identifiable different than their prey because of preferential use of one ...

  2. Accurate feature detection and estimation using nonlinear and multiresolution analysis

    NASA Astrophysics Data System (ADS)

    Rudin, Leonid; Osher, Stanley

    1994-11-01

    A program for feature detection and estimation using nonlinear and multiscale analysis was completed. The state-of-the-art edge detection was combined with multiscale restoration (as suggested by the first author) and robust results in the presence of noise were obtained. Successful applications to numerous images of interest to DOD were made. Also, a new market in the criminal justice field was developed, based in part, on this work.

  3. Reduction procedures for accurate analysis of MSX surveillance experiment data

    NASA Technical Reports Server (NTRS)

    Gaposchkin, E. Mike; Lane, Mark T.; Abbot, Rick I.

    1994-01-01

    Technical challenges of the Midcourse Space Experiment (MSX) science instruments require careful characterization and calibration of these sensors for analysis of surveillance experiment data. Procedures for reduction of Resident Space Object (RSO) detections will be presented which include refinement and calibration of the metric and radiometric (and photometric) data and calculation of a precise MSX ephemeris. Examples will be given which support the reduction, and these are taken from ground-test data similar in characteristics to the MSX sensors and from the IRAS satellite RSO detections. Examples to demonstrate the calculation of a precise ephemeris will be provided from satellites in similar orbits which are equipped with S-band transponders.

  4. Accurate Peptide Fragment Mass Analysis: Multiplexed Peptide Identification and Quantification

    PubMed Central

    Weisbrod, Chad R.; Eng, Jimmy K.; Hoopmann, Michael R.; Baker, Tahmina; Bruce, James E.

    2012-01-01

    FT All Reaction Monitoring (FT-ARM) is a novel approach for the identification and quantification of peptides that relies upon the selectivity of high mass accuracy data and the specificity of peptide fragmentation patterns. An FT-ARM experiment involves continuous, data-independent, high mass accuracy MS/MS acquisition spanning a defined m/z range. Custom software was developed to search peptides against the multiplexed fragmentation spectra by comparing theoretical or empirical fragment ions against every fragmentation spectrum across the entire acquisition. A dot product score is calculated against each spectrum in order to generate a score chromatogram used for both identification and quantification. Chromatographic elution profile characteristics are not used to cluster precursor peptide signals to their respective fragment ions. FT-ARM identifications are demonstrated to be complementary to conventional data-dependent shotgun analysis, especially in cases where the data-dependent method fails due to fragmenting multiple overlapping precursors. The sensitivity, robustness and specificity of FT-ARM quantification are shown to be analogous to selected reaction monitoring-based peptide quantification with the added benefit of minimal assay development. Thus, FT-ARM is demonstrated to be a novel and complementary data acquisition, identification, and quantification method for the large scale analysis of peptides. PMID:22288382

  5. Stable isotopic analysis of human diet in the Marianas Archipelago, western Pacific.

    PubMed

    Ambrose, S H; Butler, B M; Hanson, D B; Hunter-Anderson, R L; Krueger, H W

    1997-11-01

    Proportions of marine vs. terrestrial resources in prehistoric human diets in the southern Mariana Islands (Guam, Rota, Saipan), Micronesia, have been estimated by analysis of stable isotope ratios of carbon and nitrogen in bone collagen and of carbon in apatite. The isotopic composition of marine and terrestrial food resources from the Marianas have also been determined. Experimental evidence shows that collagen carbon isotopes mainly reflect those of dietary protein sources and thus overestimate the contribution of marine animal foods. Marine protein consumption apparently ranges from approximately 20% to approximately 50% on these islands. Experiments also demonstrate the carbon isotope ratio of bone apatite carbonate accurately reflects that of the whole diet. Carbonate carbon isotope data suggest some individuals consumed significant amounts of 13C-enriched (C4) plants or seaweeds. Sugar cane is an indigenous C4 crop and seaweeds are eaten throughout the Pacific, but they have not been considered by archaeologists to have been prehistoric dietary staples. Apatite carbon isotope analysis has apparently identified previously unrecognized prehistoric dietary adaptations in the Mariana Islands, but this must be confirmed by archaeobotanical evidence.

  6. Active contour approach for accurate quantitative airway analysis

    NASA Astrophysics Data System (ADS)

    Odry, Benjamin L.; Kiraly, Atilla P.; Slabaugh, Greg G.; Novak, Carol L.; Naidich, David P.; Lerallut, Jean-Francois

    2008-03-01

    Chronic airway disease causes structural changes in the lungs including peribronchial thickening and airway dilatation. Multi-detector computed tomography (CT) yields detailed near-isotropic images of the lungs, and thus the potential to obtain quantitative measurements of lumen diameter and airway wall thickness. Such measurements would allow standardized assessment, and physicians to diagnose and locate airway abnormalities, adapt treatment, and monitor progress over time. However, due to the sheer number of airways per patient, systematic analysis is infeasible in routine clinical practice without automation. We have developed an automated and real-time method based on active contours to estimate both airway lumen and wall dimensions; the method does not require manual contour initialization but only a starting point on the targeted airway. While the lumen contour segmentation is purely region-based, the estimation of the outer diameter considers the inner wall segmentation as well as local intensity variation, in order anticipate the presence of nearby arteries and exclude them. These properties make the method more robust than the Full-Width Half Maximum (FWHM) approach. Results are demonstrated on a phantom dataset with known dimensions and on a human dataset where the automated measurements are compared against two human operators. The average error on the phantom measurements was 0.10mm and 0.14mm for inner and outer diameters, showing sub-voxel accuracy. Similarly, the mean variation from the average manual measurement was 0.14mm and 0.18mm for inner and outer diameters respectively.

  7. Use of Stable Isotopes in Forensic Analysis of Microorganisms

    SciTech Connect

    Kreuzer-Martin, Helen W.; Hegg, Eric L.

    2012-01-18

    The use of isotopic signatures for forensic analysis of biological materials is well-established, and the same general principles that apply to interpretation of stable isotope content of C, N, O, and H apply to the analysis of microorganisms. Heterotrophic microorganisms derive their isotopic content from their growth substrates, which are largely plant and animal products, and the water in their culture medium. Thus the isotope signatures of microbes are tied to their growth environment. The C, N, O, and H isotope ratios of spores have been demonstrated to constitute highly discriminating signatures for sample matching. They can rule out specific samples of media and/or water as possible production media, and can predict isotope ratio ranges of the culture media and water used to produce a given sample. These applications have been developed and tested through analyses of approximately 250 samples of Bacillus subtilis spores and over 500 samples of culture media, providing a strong statistical basis for data interpretation. A Bayesian statistical framework for integrating stable isotope data with other types of signatures derived from microorganisms has been able to characterize the culture medium used to produce spores of various Bacillus species, leveraging isotopic differences in different medium types and demonstrating the power of data integration for forensic investigations.

  8. Accurate determination of Curium and Californium isotopic ratios by inductively coupled plasma quadrupole mass spectrometry (ICP-QMS) in 248Cm samples for transmutation studies

    SciTech Connect

    Gourgiotis, A.; Isnard, H.; Aubert, M.; Dupont, E.; AlMahamid, I.; Cassette, P.; Panebianco, S.; Letourneau, A.; Chartier, F.; Tian, G.; Rao, L.; Lukens, W.

    2011-02-01

    The French Atomic Energy Commission has carried out several experiments including the mini-INCA (INcineration of Actinides) project for the study of minor-actinide transmutation processes in high intensity thermal neutron fluxes, in view of proposing solutions to reduce the radiotoxicity of long-lived nuclear wastes. In this context, a Cm sample enriched in {sup 248}Cm ({approx}97 %) was irradiated in thermal neutron flux at the High Flux Reactor (HFR) of the Laue-Langevin Institute (ILL). This work describes a quadrupole ICP-MS (ICP-QMS) analytical procedure for precise and accurate isotopic composition determination of Cm before sample irradiation and of Cm and Cf after sample irradiation. The factors that affect the accuracy and reproducibility of isotopic ratio measurements by ICP-QMS, such as peak centre correction, detector dead time, mass bias, abundance sensitivity and hydrides formation, instrumental background, and memory blank were carefully evaluated and corrected. Uncertainties of the isotopic ratios, taking into account internal precision of isotope ratio measurements, peak tailing, and hydrides formations ranged from 0.3% to 1.3%. This uncertainties range is quite acceptable for the nuclear data to be used in transmutation studies.

  9. Isotope ratio analysis of individual sub-micrometer plutonium particles with inductively coupled plasma mass spectrometry.

    PubMed

    Esaka, Fumitaka; Magara, Masaaki; Suzuki, Daisuke; Miyamoto, Yutaka; Lee, Chi-Gyu; Kimura, Takaumi

    2010-12-15

    Information on plutonium isotope ratios in individual particles is of great importance for nuclear safeguards, nuclear forensics and so on. Although secondary ion mass spectrometry (SIMS) is successfully utilized for the analysis of individual uranium particles, the isobaric interference of americium-241 to plutonium-241 makes difficult to obtain accurate isotope ratios in individual plutonium particles. In the present work, an analytical technique by a combination of chemical separation and inductively coupled plasma mass spectrometry (ICP-MS) is developed and applied to isotope ratio analysis of individual sub-micrometer plutonium particles. The ICP-MS results for individual plutonium particles prepared from a standard reference material (NBL SRM-947) indicate that the use of a desolvation system for sample introduction improves the precision of isotope ratios. In addition, the accuracy of the (241)Pu/(239)Pu isotope ratio is much improved, owing to the chemical separation of plutonium and americium. In conclusion, the performance of the proposed ICP-MS technique is sufficient for the analysis of individual plutonium particles. PMID:21111176

  10. Isotope ratio analysis of individual sub-micrometer plutonium particles with inductively coupled plasma mass spectrometry.

    PubMed

    Esaka, Fumitaka; Magara, Masaaki; Suzuki, Daisuke; Miyamoto, Yutaka; Lee, Chi-Gyu; Kimura, Takaumi

    2010-12-15

    Information on plutonium isotope ratios in individual particles is of great importance for nuclear safeguards, nuclear forensics and so on. Although secondary ion mass spectrometry (SIMS) is successfully utilized for the analysis of individual uranium particles, the isobaric interference of americium-241 to plutonium-241 makes difficult to obtain accurate isotope ratios in individual plutonium particles. In the present work, an analytical technique by a combination of chemical separation and inductively coupled plasma mass spectrometry (ICP-MS) is developed and applied to isotope ratio analysis of individual sub-micrometer plutonium particles. The ICP-MS results for individual plutonium particles prepared from a standard reference material (NBL SRM-947) indicate that the use of a desolvation system for sample introduction improves the precision of isotope ratios. In addition, the accuracy of the (241)Pu/(239)Pu isotope ratio is much improved, owing to the chemical separation of plutonium and americium. In conclusion, the performance of the proposed ICP-MS technique is sufficient for the analysis of individual plutonium particles.

  11. Isotope analysis in the transmission electron microscope

    NASA Astrophysics Data System (ADS)

    Susi, Toma; Hofer, Christoph; Argentero, Giacomo; Leuthner, Gregor T.; Pennycook, Timothy J.; Mangler, Clemens; Meyer, Jannik C.; Kotakoski, Jani

    2016-10-01

    The Ångström-sized probe of the scanning transmission electron microscope can visualize and collect spectra from single atoms. This can unambiguously resolve the chemical structure of materials, but not their isotopic composition. Here we differentiate between two isotopes of the same element by quantifying how likely the energetic imaging electrons are to eject atoms. First, we measure the displacement probability in graphene grown from either 12C or 13C and describe the process using a quantum mechanical model of lattice vibrations coupled with density functional theory simulations. We then test our spatial resolution in a mixed sample by ejecting individual atoms from nanoscale areas spanning an interface region that is far from atomically sharp, mapping the isotope concentration with a precision better than 20%. Although we use a scanning instrument, our method may be applicable to any atomic resolution transmission electron microscope and to other low-dimensional materials.

  12. Isotopic abundance in atom trap trace analysis

    DOEpatents

    Lu, Zheng-Tian; Hu, Shiu-Ming; Jiang, Wei; Mueller, Peter

    2014-03-18

    A method and system for detecting ratios and amounts of isotopes of noble gases. The method and system is constructed to be able to measure noble gas isotopes in water and ice, which helps reveal the geological age of the samples and understand their movements. The method and system uses a combination of a cooled discharge source, a beam collimator, a beam slower and magneto-optic trap with a laser to apply resonance frequency energy to the noble gas to be quenched and detected.

  13. Isotopic ratio correlation for the isotopic composition analysis of plutonium in Am-Pu mixed samples having high americium content.

    PubMed

    Patra, Sabyasachi; Agarwal, Chhavi; Chaudhury, Sanhita; Newton Nathaniel, T; Gathibandhe, M; Goswami, A

    2013-08-01

    Interference of high amount of americium in the plutonium isotopic composition analysis has been studied by simulating gamma-ray spectra for Am-Pu samples over a wide composition range (5-97% (241)Am) for both power and research reactor grade plutonium. An alternate way for isotopic composition analysis has been proposed by correlating the isotopic ratios available in our old database with the experimentally obtained (241)Pu/(239)Pu isotopic ratio. The proposed method has been validated using simulated spectra of known isotopic compositions.

  14. Method for isotopic analysis of chlorinated organic compounds

    DOEpatents

    Holt, Ben D.; Sturchio, Neil C.

    1999-01-01

    The present invention provides a method for preparing a VOC sample for carbon and chlorine isotope ratio analysis by mass spectrometer. A VOC sample is placed in a combustion tube and reacted with CuO to form CO.sub.2 and CuCl. The CO.sub.2 is then extracted and analyzed for the carbon isotope ratio. The CuCl is separated from the excess CuO and reacted with CH.sub.3 I to form CH.sub.3 Cl, extracted and analyzed for chlorine isotope ratio.

  15. Method for isotopic analysis of chlorinated organic compounds

    DOEpatents

    Holt, B.D.; Sturchio, N.C.

    1999-08-24

    The present invention provides a method for preparing a VOC sample for carbon and chlorine isotope ratio analysis by mass spectrometer. A VOC sample is placed in a combustion tube and reacted with CuO to form CO{sub 2} and CuCl. The CO{sub 2} is then extracted and analyzed for the carbon isotope ratio. The CuCl is separated from the excess CuO and reacted with CH{sub 3}I to form CH{sub 3}Cl, extracted and analyzed for chlorine isotope ratio. 9 figs.

  16. Identification of gasoline lead in children's blood using isotopic analysis.

    PubMed

    Tera, O; Schwartzman, D W; Watkins, T R

    1985-01-01

    The isotopic composition and concentrations of lead were measured, using mass spectrometric analysis, in blood drawn from 14 young children who lived in Washington, D.C. The isotopic composition of lead in ambient air, which reflects the changing sources of gasoline lead, was also determined for the period of sampling. Blood lead concentrations ranged from 4.38 to 24.7 micrograms/100 g blood. Based on linear patterns that involved ratios of all four isotopes consistent with two component mixing, we estimate a minimum contribution of recent gasoline lead ranging from 0 to 57% of the blood lead burden.

  17. Micro-scale (1.5 microm) sulphur isotope analysis of contemporary and early Archean pyrite.

    PubMed

    Nishizawa, Manabu; Maruyama, Shigenori; Urabe, Tetsuro; Takahata, Naoto; Sano, Yuji

    2010-05-30

    We present a method for in situ sulphur (S) isotopic analysis of significantly small areas (1.5 microm in diameter) in pyrite using secondary ion mass spectrometry (NanoSIMS) to interpret microbial sulphur metabolism in the early earth. We evaluated the precision and accuracy of S isotopic ratios obtained by this method using hydrothermal pyrite samples with homogeneous S isotopic ratios. The internal precision of the delta(34)S value was 1.5 per thousand at the level of 1 sigma of standard error (named 1SE) for a single spot, while the external reproducibility was estimated to be 1.6 per thousand at the level of 1 sigma of standard deviation (named 1SD, n = 25). For each separate sample, the average delta(34)S value was comparable with that measured by a conventional method, and the accuracy was better than 2.3 per thousand. Consequently, the in situ method is sufficiently accurate and precise to detect the S isotopic variations of small sample of the pyrite (less than 20 microm) that occurs ubiquitously in ancient sedimentary rocks. This method was applied to measure the S isotopic distribution of pyrite within black chert fragments in early Archean sandstone. The pyrite had isotopic zoning with a (34)S-depleted core and (34)S-enriched rim, suggesting isotopic evolution of the source H(2)S from -15 to -5 per thousand. Production of H(2)S by microbial sulphate reduction (MSR) in a closed system provides a possible explanation for both the (34)S-depleted initial H(2)S and the progressive increase in the delta(34)S(H2S) value. Although more extensive data are necessary to strengthen the explanation for the origin of the MSR, the results show that the S isotopic distribution within pyrite crystals may be a key tracer for MSR activity in the early earth.

  18. Micro-scale (1.5 microm) sulphur isotope analysis of contemporary and early Archean pyrite.

    PubMed

    Nishizawa, Manabu; Maruyama, Shigenori; Urabe, Tetsuro; Takahata, Naoto; Sano, Yuji

    2010-05-30

    We present a method for in situ sulphur (S) isotopic analysis of significantly small areas (1.5 microm in diameter) in pyrite using secondary ion mass spectrometry (NanoSIMS) to interpret microbial sulphur metabolism in the early earth. We evaluated the precision and accuracy of S isotopic ratios obtained by this method using hydrothermal pyrite samples with homogeneous S isotopic ratios. The internal precision of the delta(34)S value was 1.5 per thousand at the level of 1 sigma of standard error (named 1SE) for a single spot, while the external reproducibility was estimated to be 1.6 per thousand at the level of 1 sigma of standard deviation (named 1SD, n = 25). For each separate sample, the average delta(34)S value was comparable with that measured by a conventional method, and the accuracy was better than 2.3 per thousand. Consequently, the in situ method is sufficiently accurate and precise to detect the S isotopic variations of small sample of the pyrite (less than 20 microm) that occurs ubiquitously in ancient sedimentary rocks. This method was applied to measure the S isotopic distribution of pyrite within black chert fragments in early Archean sandstone. The pyrite had isotopic zoning with a (34)S-depleted core and (34)S-enriched rim, suggesting isotopic evolution of the source H(2)S from -15 to -5 per thousand. Production of H(2)S by microbial sulphate reduction (MSR) in a closed system provides a possible explanation for both the (34)S-depleted initial H(2)S and the progressive increase in the delta(34)S(H2S) value. Although more extensive data are necessary to strengthen the explanation for the origin of the MSR, the results show that the S isotopic distribution within pyrite crystals may be a key tracer for MSR activity in the early earth. PMID:20411578

  19. Basalt Pb isotope analysis and the prehistoric settlement of Polynesia.

    PubMed

    Weisler, M I; Woodhead, J D

    1995-03-14

    The prehistoric settlement of the Pacific Ocean has intrigued scholars and stimulated anthropological debate for the past two centuries. Colonized over a few millennia during the mid to late Holocene, the islands of the Pacific--displaying a wide diversity of geological and biotic variability--provided the stage for endless "natural experiments" in human adaptation. Crucial to understanding the evolution and transformation of island societies is documenting the relative degree of interisland contacts after island colonization. In the western Pacific, ideal materials for archaeologically documenting interisland contact--obsidian, pottery, and shell ornaments--are absent or of limited geographic distribution in Polynesia. Consequently, archaeologists have relied increasingly on fine-grained basalt artifacts as a means for documenting colonization routes and subsequent interisland contacts. Routinely used x-ray fluorescence characterization of oceanic island basalt has some problems for discriminating source rocks and artifacts in provenance studies. The variation in trace and major element abundances is largely controlled by near-surface magma-chamber processes and is broadly similar between most oceanic islands. We demonstrate that Pb isotope analysis accurately discriminates rock source and is an excellent technique for charting the scale, frequency, and temporal span of imported fine-grained basalt artifacts found throughout Polynesia. The technique adds another tool for addressing evolutionary models of interaction, isolation, and cultural divergence in the eastern Pacific. PMID:7892194

  20. Basalt Pb isotope analysis and the prehistoric settlement of Polynesia.

    PubMed

    Weisler, M I; Woodhead, J D

    1995-03-14

    The prehistoric settlement of the Pacific Ocean has intrigued scholars and stimulated anthropological debate for the past two centuries. Colonized over a few millennia during the mid to late Holocene, the islands of the Pacific--displaying a wide diversity of geological and biotic variability--provided the stage for endless "natural experiments" in human adaptation. Crucial to understanding the evolution and transformation of island societies is documenting the relative degree of interisland contacts after island colonization. In the western Pacific, ideal materials for archaeologically documenting interisland contact--obsidian, pottery, and shell ornaments--are absent or of limited geographic distribution in Polynesia. Consequently, archaeologists have relied increasingly on fine-grained basalt artifacts as a means for documenting colonization routes and subsequent interisland contacts. Routinely used x-ray fluorescence characterization of oceanic island basalt has some problems for discriminating source rocks and artifacts in provenance studies. The variation in trace and major element abundances is largely controlled by near-surface magma-chamber processes and is broadly similar between most oceanic islands. We demonstrate that Pb isotope analysis accurately discriminates rock source and is an excellent technique for charting the scale, frequency, and temporal span of imported fine-grained basalt artifacts found throughout Polynesia. The technique adds another tool for addressing evolutionary models of interaction, isolation, and cultural divergence in the eastern Pacific.

  1. Basalt Pb isotope analysis and the prehistoric settlement of Polynesia.

    PubMed Central

    Weisler, M I; Woodhead, J D

    1995-01-01

    The prehistoric settlement of the Pacific Ocean has intrigued scholars and stimulated anthropological debate for the past two centuries. Colonized over a few millennia during the mid to late Holocene, the islands of the Pacific--displaying a wide diversity of geological and biotic variability--provided the stage for endless "natural experiments" in human adaptation. Crucial to understanding the evolution and transformation of island societies is documenting the relative degree of interisland contacts after island colonization. In the western Pacific, ideal materials for archaeologically documenting interisland contact--obsidian, pottery, and shell ornaments--are absent or of limited geographic distribution in Polynesia. Consequently, archaeologists have relied increasingly on fine-grained basalt artifacts as a means for documenting colonization routes and subsequent interisland contacts. Routinely used x-ray fluorescence characterization of oceanic island basalt has some problems for discriminating source rocks and artifacts in provenance studies. The variation in trace and major element abundances is largely controlled by near-surface magma-chamber processes and is broadly similar between most oceanic islands. We demonstrate that Pb isotope analysis accurately discriminates rock source and is an excellent technique for charting the scale, frequency, and temporal span of imported fine-grained basalt artifacts found throughout Polynesia. The technique adds another tool for addressing evolutionary models of interaction, isolation, and cultural divergence in the eastern Pacific. PMID:7892194

  2. High Resolution Gamma Ray Analysis of Medical Isotopes

    NASA Astrophysics Data System (ADS)

    Chillery, Thomas

    2015-10-01

    Compton-suppressed high-purity Germanium detectors at the University of Massachusetts Lowell have been used to study medical radioisotopes produced at Brookhaven Linac Isotope Producer (BLIP), in particular isotopes such as Pt-191 used for cancer therapy in patients. The ability to precisely analyze the concentrations of such radio-isotopes is essential for both production facilities such as Brookhaven and consumer hospitals across the U.S. Without accurate knowledge of the quantities and strengths of these isotopes, it is possible for doctors to administer incorrect dosages to patients, thus leading to undesired results. Samples have been produced at Brookhaven and shipped to UML, and the advanced electronics and data acquisition capabilities at UML have been used to extract peak areas in the gamma decay spectra. Levels of Pt isotopes in diluted samples have been quantified, and reaction cross-sections deduced from the irradiation parameters. These provide both cross checks with published work, as well as a rigorous quantitative framework with high quality state-of-the-art detection apparatus in use in the experimental nuclear physics community.

  3. Light stable isotope analysis of meteorites by ion microprobe

    NASA Technical Reports Server (NTRS)

    Mcsween, Harry Y., Jr.

    1994-01-01

    The main goal was to develop the necessary secondary ion mass spectrometer (SIMS) techniques to use a Cameca ims-4f ion microprobe to measure light stable isotope ratios (H, C, O and S) in situ and in non-conducting mineral phases. The intended application of these techniques was the analysis of meteorite samples, although the techniques that have been developed are equally applicable to the investigation of terrestrial samples. The first year established techniques for the analysis of O isotope ratios (delta O-18 and delta O-17) in conducting mineral phases and the measurement of S isotope ratios (delta S-34) in a variety of sulphide phases. In addition, a technique was developed to measure delta S-34 values in sulphates, which are insulators. Other research undertaken in the first year resulted in SIMS techniques for the measurement of wide variety of trace elements in carbonate minerals, with the aim of understanding the nature of alteration fluids in carbonaceous chondrites. In the second year we developed techniques for analyzing O isotope ratios in nonconducting mineral phases. These methods are potentially applicable to the measurement of other light stable isotopes such as H, C and S in insulators. Also, we have further explored the analytical techniques used for the analysis of S isotopes in sulphides by analyzing troilite in a number of L and H ordinary chondrites. This was done to see if there was any systematic differences with petrological type.

  4. Isotopic analysis of cometary organic matter

    NASA Astrophysics Data System (ADS)

    Kerridge, J. F.

    1991-04-01

    Carbon isotope ratios have been measured for CN in the coma of Comet Halley and for several CHON particles emitted by Halley. Of these, only the CHON-particle data may be reasonably related to organic matter in the cometary nucleus, but the true range of (C-13)/(C-12) values in those particles is quite uncertain. The D/H ratio in H2O in the Halley coma resembles that in Titan/Uranus.

  5. Isotopic analysis of cometary organic matter

    NASA Technical Reports Server (NTRS)

    Kerridge, John F.

    1991-01-01

    Carbon isotope ratios have been measured for CN in the coma of Comet Halley and for several CHON particles emitted by Halley. Of these, only the CHON-particle data may be reasonably related to organic matter in the cometary nucleus, but the true range of (C-13)/(C-12) values in those particles is quite uncertain. The D/H ratio in H2O in the Halley coma resembles that in Titan/Uranus.

  6. Direct uranium isotope ratio analysis of single micrometer-sized glass particles

    PubMed Central

    Kappel, Stefanie; Boulyga, Sergei F.; Prohaska, Thomas

    2012-01-01

    We present the application of nanosecond laser ablation (LA) coupled to a ‘Nu Plasma HR’ multi collector inductively coupled plasma mass spectrometer (MC-ICP-MS) for the direct analysis of U isotope ratios in single, 10–20 μm-sized, U-doped glass particles. Method development included studies with respect to (1) external correction of the measured U isotope ratios in glass particles, (2) the applied laser ablation carrier gas (i.e. Ar versus He) and (3) the accurate determination of lower abundant 236U/238U isotope ratios (i.e. 10−5). In addition, a data processing procedure was developed for evaluation of transient signals, which is of potential use for routine application of the developed method. We demonstrate that the developed method is reliable and well suited for determining U isotope ratios of individual particles. Analyses of twenty-eight S1 glass particles, measured under optimized conditions, yielded average biases of less than 0.6% from the certified values for 234U/238U and 235U/238U ratios. Experimental results obtained for 236U/238U isotope ratios deviated by less than −2.5% from the certified values. Expanded relative total combined standard uncertainties Uc (k = 2) of 2.6%, 1.4% and 5.8% were calculated for 234U/238U, 235U/238U and 236U/238U, respectively. PMID:22595724

  7. Direct uranium isotope ratio analysis of single micrometer-sized glass particles.

    PubMed

    Kappel, Stefanie; Boulyga, Sergei F; Prohaska, Thomas

    2012-11-01

    We present the application of nanosecond laser ablation (LA) coupled to a 'Nu Plasma HR' multi collector inductively coupled plasma mass spectrometer (MC-ICP-MS) for the direct analysis of U isotope ratios in single, 10-20 μm-sized, U-doped glass particles. Method development included studies with respect to (1) external correction of the measured U isotope ratios in glass particles, (2) the applied laser ablation carrier gas (i.e. Ar versus He) and (3) the accurate determination of lower abundant (236)U/(238)U isotope ratios (i.e. 10(-5)). In addition, a data processing procedure was developed for evaluation of transient signals, which is of potential use for routine application of the developed method. We demonstrate that the developed method is reliable and well suited for determining U isotope ratios of individual particles. Analyses of twenty-eight S1 glass particles, measured under optimized conditions, yielded average biases of less than 0.6% from the certified values for (234)U/(238)U and (235)U/(238)U ratios. Experimental results obtained for (236)U/(238)U isotope ratios deviated by less than -2.5% from the certified values. Expanded relative total combined standard uncertainties U(c) (k = 2) of 2.6%, 1.4% and 5.8% were calculated for (234)U/(238)U, (235)U/(238)U and (236)U/(238)U, respectively.

  8. Accurate determination of ochratoxin A in Korean fermented soybean paste by isotope dilution-liquid chromatography tandem mass spectrometry.

    PubMed

    Ahn, Seonghee; Lee, Suyoung; Lee, Joonhee; Kim, Byungjoo

    2016-01-01

    Ochratoxin A (OTA), a naturally occurring mycotoxin, has been frequently detected in doenjang, a traditional fermented soybean paste, when it is fermented under improper conditions. Reliable screening of OTA in traditional fermented soybean paste (doenjang) is a special food-safety issue in Korea. Our laboratory, the National Metrology Institute of Korea, established an isotope dilution-liquid chromatography tandem mass spectrometry (ID-LC/MS/MS) method as a higher-order reference method to be used for SI-traceable value-assignment of OTA in certified reference materials (CRMs). (13)C20-OTA was used as an internal standard. Sample preparation conditions and LC/MS measurement parameters were optimised for this purpose. The analytical method was validated by measuring samples fortified with OTA at various levels. Repeatability and reproducibility studies showed that the ID-LC/MS/MS method is reliable and reproducible within 2% relative standard deviation. The analytical method was applied to determine OTA in various commercial doenjang products and home-made doenjang products.

  9. Stable-Isotopic Analysis of Porcine, Bovine, and Ovine Heparins

    PubMed Central

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

    2014-01-01

    The assessment of provenance of heparin is becoming a major concern for the pharmaceutical industry and its regulatory bodies. Batch-specific [carbon (δ13C), nitrogen (δ15N), oxygen (δ18O), sulfur (δ34S), and hydrogen (δD)] stable-isotopic compositions of five different animal-derived heparins were performed. Measurements readily allowed their differentiation into groups and/or subgroups based on their isotopic provenance. Principle component analysis showed that a bivariate plot of δ13C and δ18O is the best single, bivariate plot that results in the maximum discrimination ability when only two stable isotopes are used to describe the variation in the data set. Stable-isotopic analyses revealed that (i) stable-isotope measurements on these highly-sulfated polysaccharide (MW ~15 kDa) natural products (“biologics”) were feasible; (ii) in bivariate plots, the δ13C versus δ18O plot reveals a well-defined relationship for source differentiation of hogs raised in the US from hogs raised in Europe and China; (iii) the δD versus δ18O plot revealed the most well-defined relationship for source differentiation based on the hydrologic-environmental isotopes of water (D/H and 18O/16O), and (iv) the δ15N versus δ18O and δ34S versus δ18O relationships are both very similar, possibly reflecting the food sources used by the different heparin producers. PMID:25186630

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

    PubMed

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

    2015-02-01

    The assessment of provenance of heparin is becoming a major concern for the pharmaceutical industry and its regulatory bodies. Batch-specific [carbon (δ(13) C), nitrogen (δ(15) N), oxygen (δ(18) O), sulfur (δ(34) S), and hydrogen (δD)] stable isotopic compositions of five different animal-derived heparins were performed. Measurements readily allowed their differentiation into groups and/or subgroups based on their isotopic provenance. Principle component analysis showed that a bivariate plot of δ(13) C and δ(18) O is the best single, bivariate plot that results in the maximum discrimination ability when only two stable isotopes are used to describe the variation in the data set. Stable isotopic analyses revealed that (1) stable isotope measurements on these highly sulfated polysaccharide (molecular weight ∼15 kDa) natural products ("biologics") were feasible; (2) in bivariate plots, the δ(13) C versus δ(18) O plot reveals a well-defined relationship for source differentiation of hogs raised in the United States from hogs raised in Europe and China; (3) the δD versus δ(18) O plot revealed the most well-defined relationship for source differentiation based on the hydrologic environmental isotopes of water (D/H and (18) O/(16) O); and (4) the δ(15) N versus δ(18) O and δ(34) S versus δ(18) O relationships are both very similar, possibly reflecting the food sources used by the different heparin producers. PMID:25186630

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

    PubMed

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

    2015-02-01

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

  12. Enantioselective stable isotope analysis (ESIA) of polar Herbicides

    NASA Astrophysics Data System (ADS)

    Maier, Michael; Qiu, Shiran; Elsner, Martin

    2013-04-01

    The complexity of aquatic systems makes it challenging to assess the environmental fate of chiral micropolutants. As an example, chiral herbicides are frequently detected in the environment (Buser and Muller, 1998); however, hydrological data is needed to determine their degradability from concentration measurements. Otherwise declining concentrations cannot unequivocally be attributed to degradation, but could also be caused by dilution effects. In contrast, isotope ratios or enantiomeric ratios are elegant alternatives that are independent of dilution and can even deliver insights into reaction mechanisms. To combine the advantages of both approaches we developed an enatioselective stable isotope analysis (ESIA) method to investigate the fate of the chiral herbicides 4-CPP ((RS)-2-(4-chlorophenoxy)-propionic acid), mecoprop (2-(4-Chloro-2-methylphenoxy)-propionic acid) and dichlorprop (2-(2,4-Dichlorophenoxy)-propionic acid). After testing the applicable concentration range of the method, enantioselective isotope fractionation was investigated by microbial degradation using dichlorprop as a model compound. The method uses enantioselective gas-chromatography (GC) to separate enantiomers. Subsequently samples are combusted online to CO2 and carbon isotope ratios are determined for each enantiomer by isotope-ratio-mass-spectrometry (IRMS). Because the analytes contain a polar carboxyl-group, samples were derivatised prior to GC-IRMS analysis with methanolic BF3 solution. Precise carbon isotope analysis (2σ ≤0.5‰) was achieved with a high sensitivity of ≥ 7 ng C that is needed on column for one analysis. Microbial degradation of the model compound dichlorprop was conducted with Delftia acidovorans MC1 and pronounced enantiomer fractionation, but no isotope fractionation was detected. The absence of isotope fractionation can be explained by two scenarios: either the degrading enzyme has no isotopic preference, or another step in the reaction without an isotopic

  13. Stable isotopic analysis of pyrogenic organic matter in soils by liquid chromatography-isotope-ratio mass spectrometry of benzene polycarboxylic acids.

    PubMed

    Yarnes, Christopher; Santos, Fernanda; Singh, Nimisha; Abiven, Samuel; Schmidt, Michael W I; Bird, Jeffrey A

    2011-12-30

    Pyrogenic organic matter (PyOM), the incomplete combustion product of organic materials, is considered stable in soils and represents a potentially important terrestrial sink for atmospheric carbon dioxide. One well-established method of measuring PyOM in the environment is as benzene polycarboxylic acids (BPCAs), a compound-specific method, which allows both qualitative and quantitative estimation of PyOM. Until now, stable isotope measurement of PyOM carbon involved measurement of the trimethylsilyl (TMS) or methyl (Me) polycarboxylic acid derivatives by gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS). However, BPCA derivatives can contain as much as 150% derivative carbon, necessitating post-analysis correction for the accurate measurement of δ¹³C values, leading to increased measurement error. Here, we describe a method for δ¹³C isotope ratio measurement and quantification of BPCAs from soil-derived PyOM, based on ion-exchange chromatography (IEC-IRMS). The reproducibility of the δ¹³C measurement of individual BPCAs by IEC-IRMS was better than 0.35‰ (1σ). The δ¹³C-BPCA analysis of PyOM in soils, including at natural and artificially enriched ¹³C-abundance, produced accurate and precise δ¹³C measurements. Analysis of samples that differed in δ¹³C by as much as 900‰ revealed carryover of <1‰ between samples. The weighted sum of individual δ¹³C-BPCA measurements was correlated with previous isotopic measurements of whole PyOM, providing complementary information for bulk isotopic measurements. We discuss potential applications of δ¹³C-BPCA measurements, including the study of turnover rates of PyOM in soils and the partitioning of PyOM sources based on photosynthetic pathways. PMID:22468329

  14. Potential of isotope analysis (C, Cl) to identify dechlorination mechanisms

    NASA Astrophysics Data System (ADS)

    Cretnik, Stefan; Thoreson, Kristen; Bernstein, Anat; Ebert, Karin; Buchner, Daniel; Laskov, Christine; Haderlein, Stefan; Shouakar-Stash, Orfan; Kliegman, Sarah; McNeill, Kristopher; Elsner, Martin

    2013-04-01

    Chloroethenes are commonly used in industrial applications, and detected as carcinogenic contaminants in the environment. Their dehalogenation is of environmental importance in remediation processes. However, a detailed understanding frequently accounted problem is the accumulation of toxic degradation products such as cis-dichloroethylene (cis-DCE) at contaminated sites. Several studies have addressed the reductive dehalogenation reactions using biotic and abiotic model systems, but a crucial question in this context has remained open: Do environmental transformations occur by the same mechanism as in their corresponding in vitro model systems? The presented study shows the potential to close this research gap using the latest developments in compound specific chlorine isotope analysis, which make it possible to routinely measure chlorine isotope fractionation of chloroethenes in environmental samples and complex reaction mixtures.1,2 In particular, such chlorine isotope analysis enables the measurement of isotope fractionation for two elements (i.e., C and Cl) in chloroethenes. When isotope values of both elements are plotted against each other, different slopes reflect different underlying mechanisms and are remarkably insensitive towards masking. Our results suggest that different microbial strains (G. lovleyi strain SZ, D. hafniense Y51) and the isolated cofactor cobalamin employ similar mechanisms of reductive dechlorination of TCE. In contrast, evidence for a different mechanism was obtained with cobaloxime cautioning its use as a model for biodegradation. The study shows the potential of the dual isotope approach as a tool to directly compare transformation mechanisms of environmental scenarios, biotic transformations, and their putative chemical lab scale systems. Furthermore, it serves as an essential reference when using the dual isotope approach to assess the fate of chlorinated compounds in the environment.

  15. Analysis of proteome dynamics in mice by isotopic labeling.

    PubMed

    Price, John C; Ghaemmaghami, Sina

    2014-01-01

    Recent advances in mass spectrometry and in vivo isotopic labeling have enabled proteome-wide analyses of protein turnover in complex organisms. Here, we describe a protocol for analyzing protein turnover rates in mouse tissues by comprehensive (15)N labeling. The procedure involves the complete isotopic labeling of blue green algae (Spirulina platensis) with (15)N and utilizing it as a source of dietary nitrogen for mice. We outline a detailed protocol for in-house production of (15)N-labeled algae, labeling of mice, and analysis of isotope incorporation kinetics by mass spectrometry. The methodology can be adapted to analyze proteome dynamics in most murine tissues and may be particularly useful in the analysis of proteostatic disruptions in mouse models of disease. PMID:24791984

  16. Enantiomeric and Isotopic Analysis of Organic Compounds in Carbonaceous Meteorites

    NASA Technical Reports Server (NTRS)

    Cooper, George

    2004-01-01

    Carbonaceous meteorites are relatively enriched in soluble organic compounds. The Murchison and Murray meteorites contain numerous compounds of interest in the study of early solar system organic chemistry and organic compounds of potential importance for the origin of life. These include: amino acids, amides, carboxylic acids, and polyols. This talk will focus on the enantiomeric and isotopic analysis of individual meteoritic compounds - primarily polyol acids. The analyses will determine if, in addition to certain amino acids from Murchison, another potentially important class of prebiotic compounds also contains enantiomeric excesses, i.e., excesses that could have contributed to the current homochirality of life. Preliminary enantiomeric and isotopic (C- 13) measurements of Murchison glyceric acid show that it is indeed extraterrestrial. C-13 and D isotope analysis of meteoritic sugar alcohols (glycerol, threitol, ribitol, etc.) has shown that they are also indigenous to the meteorite.

  17. Sectional power-law correction for the accurate determination of lutetium by isotope dilution multiple collector-inductively coupled plasma-mass spectrometry

    NASA Astrophysics Data System (ADS)

    Yuan, Hong-Lin; Gao, Shan; Zong, Chun-Lei; Dai, Meng-Ning

    2009-11-01

    In this study, we employ a sectional power-law (SPL) correction that provides accurate and precise measurements of 176Lu/ 175Lu ratios in geological samples using multiple collector-inductively coupled plasma-mass spectrometry (MC-ICP-MS). Three independent power laws were adopted based on the 176Lu/ 176Yb ratios of samples measured after chemical chromatography. Using isotope dilution (ID) techniques and the SPL correction method, the measured lutetium contents of United States Geological Survey rock standards (BHVO-1, BHVO-2, BCR-2, AGV-1, and G-2) agree well with the recommended values. Results obtained by conventional ICP-MS and INAA are generally higher than those obtained by ID-TIMS and ID-MC-ICP-MS; this discrepancy probably reflects oxide interference and inaccurate corrections.

  18. Stable isotope dilution HILIC-MS/MS method for accurate quantification of glutamic acid, glutamine, pyroglutamic acid, GABA and theanine in mouse brain tissues.

    PubMed

    Inoue, Koichi; Miyazaki, Yasuto; Unno, Keiko; Min, Jun Zhe; Todoroki, Kenichiro; Toyo'oka, Toshimasa

    2016-01-01

    In this study, we developed the stable isotope dilution hydrophilic interaction liquid chromatography with tandem mass spectrometry (HILIC-MS/MS) technique for the accurate, reasonable and simultaneous quantification of glutamic acid (Glu), glutamine (Gln), pyroglutamic acid (pGlu), γ-aminobutyric acid (GABA) and theanine in mouse brain tissues. The quantification of these analytes was accomplished using stable isotope internal standards and the HILIC separating mode to fully correct the intramolecular cyclization during the electrospray ionization. It was shown that linear calibrations were available with high coefficients of correlation (r(2)  > 0.999, range from 10 pmol/mL to 50 mol/mL). For application of the theanine intake, the determination of Glu, Gln, pGlu, GABA and theanine in the hippocampus and central cortex tissues was performed based on our developed method. In the region of the hippocampus, the concentration levels of Glu and pGlu were significantly reduced during reality-based theanine intake. Conversely, the concentration level of GABA increased. This result showed that transited theanine has an effect on the metabolic balance of Glu analogs in the hippocampus.

  19. Hg stable isotope analysis by the double-spike method.

    PubMed

    Mead, Chris; Johnson, Thomas M

    2010-06-01

    Recent publications suggest great potential for analysis of Hg stable isotope abundances to elucidate sources and/or chemical processes that control the environmental impact of mercury. We have developed a new MC-ICP-MS method for analysis of mercury isotope ratios using the double-spike approach, in which a solution containing enriched (196)Hg and (204)Hg is mixed with samples and provides a means to correct for instrumental mass bias and most isotopic fractionation that may occur during sample preparation and introduction into the instrument. Large amounts of isotopic fractionation induced by sample preparation and introduction into the instrument (e.g., by batch reactors) are corrected for. This may greatly enhance various Hg pre-concentration methods by correcting for minor fractionation that may occur during preparation and removing the need to demonstrate 100% recovery. Current precision, when ratios are normalized to the daily average, is 0.06 per thousand, 0.06 per thousand, 0.05 per thousand, and 0.05 per thousand (2sigma) for (202)Hg/(198)Hg, (201)Hg/(198)Hg, (200)Hg/(198)Hg, and (199)Hg/(198)Hg, respectively. This is slightly better than previously published methods. Additionally, this precision was attained despite the presence of large amounts of other Hg isotopes (e.g., 5.0% atom percent (198)Hg) in the spike solution; substantially better precision could be achieved if purer (196)Hg were used.

  20. Selection of Isotopes and Elements for Fuel Cycle Analysis

    SciTech Connect

    Steven J. Piet

    2009-04-01

    Fuel cycle system analysis simulations examine how the selection among fuel cycle options for reactors, fuel, separation, and waste management impact uranium ore utilization, waste masses and volumes, radiotoxicity, heat to geologic repositories, isotope-dependent proliferation resistance measures, and so forth. Previously, such simulations have tended to track only a few actinide and fission product isotopes, those that have been identified as important to a few criteria from the standpoint of recycled material or waste, taken as a whole. After accounting for such isotopes, the residual mass is often characterized as “fission product other” or “actinide other”. However, detailed assessment of separation and waste management options now require identification of key isotopes and residual mass for Group 1A/2A elements (Rb, Cs, Sr, Ba), inert gases (Kr, Xe), halogens (Br, I), lanthanides, transition metals, transuranic (TRU), uranium, actinide decay products. The paper explains the rationale for a list of 81 isotopes and chemical elements to better support separation and waste management assessment in dynamic system analysis models such as Verifiable Fuel Cycle Simulation (VISION)

  1. Advances in laser ablation MC-ICPMS isotopic analysis of rock materials

    NASA Astrophysics Data System (ADS)

    Young, E. D.

    2007-12-01

    Laser ablation multiple-collector inductively coupled plasma-source mass spectrometry (LA-MC-ICPMS) is a rapid method for obtaining high-precision isotope ratio measurements in geological samples. The method has been used with success for measuring isotope ratios of numerous elements, including Pb, Hf, Mg, Si, and Fe in terrestrial and extraterrestrial samples. It fills the gap between the highest precision obtainable with acid digestion together with MC-ICPMS and thermal ionization mass spectrometry (TIMS) and the maximum spatial resolution afforded by secondary ion mass spectrometry (SIMS). Matrix effects have been shown to be negligible for Pb isotopic analysis by LA-MC-ICPMS (Simon et al., 2007). Glass standards NBS 610, 612, and 614 have Pb/matrix ratios spanning two orders of magnitude. Our sample-standard bracketing laser ablation technique gives accurate and precise 208Pb/206Pb and 207Pb/206Pb for these glasses. The accuracy is superior to that obtained when using Tl to correct for mass fractionation. Accuracy and precision (± 0.2 ‰) for Pb in feldspars is comparable to that for double-spike TIMS. Data like these have been used to distinguish distinct sources of magmas in the Long Valley silicic magma system. LA-MC-ICPMS analyses of Mg isotope ratios in calcium-aluminum-rich inclusions (CAIs) from carbonaceous chondrite meteorites have revealed a wealth of new information about the history of these objects. A byproduct of this work has been recognition of the importance of different mass fractionation laws among three isotopes of a given element. Kinetic and equilibrium processes define distinct fractionation laws. Reservoir effects can further modify these laws. The result is that the linear coefficient β that relates the logarithms of the ratios n2/n1 and n3/n1 (ni refers to the number of atoms of isotope i) of isotopes with masses m3 > m2 > m1 is not unique. Rather, it is process dependent. In the case of Mg, this coefficient ranges from 0.521 for

  2. Trophic Hierarchies Illuminated via Amino Acid Isotopic Analysis

    PubMed Central

    Steffan, Shawn A.; Chikaraishi, Yoshito; Horton, David R.; Ohkouchi, Naohiko; Singleton, Merritt E.; Miliczky, Eugene; Hogg, David B.; Jones, Vincent P.

    2013-01-01

    Food web ecologists have long sought to characterize the trophic niches of animals using stable isotopic analysis. However, distilling trophic position from isotopic composition has been difficult, largely because of the variability associated with trophic discrimination factors (inter-trophic isotopic fractionation and routing). We circumvented much of this variability using compound-specific isotopic analysis (CSIA). We examined the 15N signatures of amino acids extracted from organisms reared in pure culture at four discrete trophic levels, across two model communities. We calculated the degree of enrichment at each trophic level and found there was a consistent trophic discrimination factor (~7.6‰). The constancy of the CSIA-derived discrimination factor permitted unprecedented accuracy in the measurement of animal trophic position. Conversely, trophic position estimates generated via bulk-15N analysis significantly underestimated trophic position, particularly among higher-order consumers. We then examined the trophic hierarchy of a free-roaming arthropod community, revealing the highest trophic position (5.07) and longest food chain ever reported using CSIA. High accuracy in trophic position estimation brings trophic function into sharper focus, providing greater resolution to the analysis of food webs. PMID:24086703

  3. Trophic spectra under the lens of amino acid isotopic analysis

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Recent advances in compound specific isotopic ratio analysis (CSIRA) have allowed researchers to measure trophic fractionation of 15N in specific amino acids, namely glutamic acid and phenylalanine. These amino acids have proven useful in food web studies because of the wide and consistent disparity...

  4. Accurate and precise quantification of atmospheric nitrate in streams draining land of various uses by using triple oxygen isotopes as tracers

    NASA Astrophysics Data System (ADS)

    Tsunogai, Urumu; Miyauchi, Takanori; Ohyama, Takuya; Komatsu, Daisuke D.; Nakagawa, Fumiko; Obata, Yusuke; Sato, Keiichi; Ohizumi, Tsuyoshi

    2016-06-01

    Land use in a catchment area has significant impacts on nitrate eluted from the catchment, including atmospheric nitrate deposited onto the catchment area and remineralised nitrate produced within the catchment area. Although the stable isotopic compositions of nitrate eluted from a catchment can be a useful tracer to quantify the land use influences on the sources and behaviour of the nitrate, it is best to determine these for the remineralised portion of the nitrate separately from the unprocessed atmospheric nitrate to obtain a more accurate and precise quantification of the land use influences. In this study, we determined the spatial distribution and seasonal variation of stable isotopic compositions of nitrate for more than 30 streams within the same watershed, the Lake Biwa watershed in Japan, in order to use 17O excess (Δ17O) of nitrate as an additional tracer to quantify the mole fraction of atmospheric nitrate accurately and precisely. The stable isotopic compositions, including Δ17O of nitrate, in precipitation (wet deposition; n = 196) sampled at the Sado-seki monitoring station were also determined for 3 years. The deposited nitrate showed large 17O excesses similar to those already reported for midlatitudes: Δ17O values ranged from +18.6 to +32.4 ‰ with a 3-year average of +26.3 ‰. However, nitrate in each inflow stream showed small annual average Δ17O values ranging from +0.5 to +3.1 ‰, which corresponds to mole fractions of unprocessed atmospheric nitrate to total nitrate from (1.8 ± 0.3) to (11.8 ± 1.8) % respectively, with an average for all inflow streams of (5.1 ± 0.5) %. Although the annual average Δ17O values tended to be smaller in accordance with the increase in annual average stream nitrate concentration from 12.7 to 106.2 µmol L-1, the absolute concentrations of unprocessed atmospheric nitrate were almost stable at (2.3 ± 1.1) µmol L-1 irrespective of the changes in population density and land use in each catchment area

  5. Discrimination of ginseng cultivation regions using light stable isotope analysis.

    PubMed

    Kim, Kiwook; Song, Joo-Hyun; Heo, Sang-Cheol; Lee, Jin-Hee; Jung, In-Woo; Min, Ji-Sook

    2015-10-01

    Korean ginseng is considered to be a precious health food in Asia. Today, thieves frequently compromise ginseng farms by pervasive theft. Thus, studies regarding the characteristics of ginseng according to growth region are required in order to deter ginseng thieves and prevent theft. In this study, 6 regions were selected on the basis of Korea regional criteria (si, gun, gu), and two ginseng-farms were randomly selected from each of the 6 regions. Then 4-6 samples of ginseng were acquired from each ginseng farm. The stable isotopic compositions of H, O, C, and N of the collected ginseng samples were analyzed. As a result, differences in the hydrogen isotope ratios could be used to distinguish regional differences, and differences in the nitrogen isotope ratios yielded characteristic information regarding the farms from which the samples were obtained. Thus, stable isotope values could be used to differentiate samples according to regional differences. Therefore, stable isotope analysis serves as a powerful tool to discriminate the regional origin of Korean ginseng samples from across Korea.

  6. Stable Isotope Ratios and the Forensic Analysis of Microorganisms

    SciTech Connect

    Kreuzer-Martin, Helen W.; Jarman, Kristin H.

    2007-06-01

    In the aftermath of the anthrax letters of 2001, researchers have been exploring various analytical signatures for the purpose of characterizing the production environment of microorganisms. One such signature is stable isotope ratios, which in heterotrophs are a function of nutrient and water sources. Here we discuss the use of stable isotope ratios in microbe forensics, using as a database the carbon, nitrogen, oxygen and hydrogen stable isotope ratios of 247 separate cultures of B. subtilis 6051 spores produced on a total of 32 different culture media. In the context of using stable isotope ratios as a signature for sample matching, we present an analysis of variation between individual samples, between cultures produced in tandem, and between cultures produced in the same medium but at different times. Additionally, we correlate the stable isotope ratios of carbon, nitrogen, oxygen, and hydrogen for growth medium nutrients or water with those of spores and show examples of how these relationships can be used to exclude nutrient or water samples as possible growth substrates for specific cultures.

  7. Stable isotope analysis of breath using the optogalvanic effect

    NASA Astrophysics Data System (ADS)

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

    1996-05-01

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

  8. STABLE CARBON ISOTOPE ANALYSIS OF SUBFOSSIL WOOD FROM AUSTRIAN ALPS

    PubMed Central

    KŁUSEK, MARZENA; PAWEŁCZYK, SŁAWOMIRA

    2015-01-01

    The presented studies were carried out in order to check the usefulness of subfossil wood for stable isotope analysis. The aim of research was also to define the optimal method of subfossil samples preparation. Subfossil samples used during the presented studies are a part of the multi-century dendrochronological scale. This chronology originates in an area situated around a small mountain lake — Schwarzersee, in Austria. The obtained results of stable carbon isotope measurements confirmed that the method of α-cellulose extraction by the application of acidic sodium chlorite and sodium hydroxide solutions removes resins and other mobile compounds from wood. Therefore, in the case of the analysed samples, the additional chemical process of extractives removing was found to be unnecessary. Studied wood samples contained an adequate proportion of α-cellulose similar to the values characteristic for the contemporary trees. This proved an adequate wood preservation which is essential for the conduction of isotopic research. PMID:26346297

  9. Extraction and carbon isotope analysis of CO 2 from scapolite in deep crustal granulites and xenoliths

    NASA Astrophysics Data System (ADS)

    Moecher, David P.; Valley, John W.; Essene, Eric J.

    1994-01-01

    Carbon isotope compositions of scapolite from granulite facies gneisses and lower crustal xenoliths document the composition and constrain the source of carbon in scapolite from the lower crust. CO 2 is extracted from scapolite without fractionating carbon isotopes by reaction with phosphoric acid at 25 or 75°C. Thus, partial yields of CO 2 from scapolite are sufficient for accurate carbon isotopic analysis. Isotopic compositions of coexisting scapolite and calcite in high-grade calc-silicate gneisses and marbles, and consideration of the crystal chemical environment of CO 3 in the scapolite structure, indicate little fractionation of 13C /12C between scapolite and calcite (0.1 ± 1.2%.) at equilibrium conditions of 650-800°C. The carbon isotope composition of CO 2 extracted from scapolite in twenty-nine samples of regional granulite facies gneisses, amphibolites, calc-silicate gneisses, and crustal xenoliths yield values of δ 13C that range from -10 to -1%. (PDB). High-grade marbles and graphitic paragneisses are precluded as major sources of carbon for scapolite in the high grade rocks analyzed in this study, as the former are isotopically enriched, and the latter isotopically depleted in 13C /12C relative to the range of isotopic compositions determined here. The δ 13C values for mafic granulites and amphibolites in granulite terranes composed of supracrustal sequences (-10.1 to -4.0%.) may reflect the isotopic composition of diagenetic carbonate present in their basaltic protoliths. The values of δ 13C for scapolite in mafic xenoliths and some granulite facies orthogneisses (-8.2 to -1.2%.) are consistent with crystallization of the scapolite from a mafic melt or derivation of CO 2 from mafic melts emplaced in the lower crust or upper mantle. The values of δ 13C for scapolites from calc-silicate gneisses and calc-silicate xenoliths (-10.0 to -2.9%.) may result from depletion of 13C /12C as a result of decarbonation of calcite-bearing protoliths during

  10. Advancement and application of gas chromatography isotope ratio mass spectrometry techniques for atmospheric trace gas analysis

    NASA Astrophysics Data System (ADS)

    Giebel, Brian M.

    2011-12-01

    The use of gas chromatography isotope ratio mass spectrometry (GC-IRMS) for compound specific stable isotope analysis is an underutilized technique because of the complexity of the instrumentation and high analytical costs. However stable isotopic data, when coupled with concentration measurements, can provide additional information on a compounds production, transformation, loss, and cycling within the biosphere and atmosphere. A GC-IRMS system was developed to accurately and precisely measure delta13C values for numerous oxygenated volatile organic compounds having natural and anthropogenic sources. The OVOCs include methanol, ethanol, acetone, methyl ethyl ketone, 2-pentanone, and 3-pentanone. Guided by the requirements for analysis of trace components in air, the GC-IRMS system was developed with the goals of increasing sensitivity, reducing dead-volume and peak band broadening, optimizing combustion and water removal, and decreasing the split ratio to the IRMS. The technique relied on a two-stage preconcentration system, a low-volume capillary reactor and water trap, and a balanced reference gas delivery system. Measurements were performed on samples collected from two distinct sources (i.e. biogenic and vehicle emissions) and ambient air collected from downtown Miami and Everglades National Park. However, the instrumentation and the method have the capability to analyze a variety of source and ambient samples. The measured isotopic signatures that were obtained from source and ambient samples provide a new isotopic constraint for atmospheric chemists and can serve as a new way to evaluate their models and budgets for many OVOCs. In almost all cases, OVOCs emitted from fuel combustion were enriched in 13C when compared to the natural emissions of plants. This was particularly true for ethanol gas emitted in vehicle exhaust, which was observed to have a uniquely enriched isotopic signature that was attributed to ethanol's corn origin and use as an alternative

  11. Isotopic disproportionation during hydrogen isotopic analysis of nitrogen-bearing organic compounds

    USGS Publications Warehouse

    Nair, Sreejesh; Geilmann, Heike; Coplen, Tyler B.; Qi, Haiping; Gehre, Matthias; Schimmelmann, Arndt; Brand, Willi A.

    2015-01-01

    Rationale High-precision hydrogen isotope ratio analysis of nitrogen-bearing organic materials using high-temperature conversion (HTC) techniques has proven troublesome in the past. Formation of reaction products other than molecular hydrogen (H2) has been suspected as a possible cause of incomplete H2 yield and hydrogen isotopic fractionation. Methods The classical HTC reactor setup and a modified version including elemental chromium, both operated at temperatures in excess of 1400 °C, have been compared using a selection of nitrogen-bearing organic compounds, including caffeine. A focus of the experiments was to avoid or suppress hydrogen cyanide (HCN) formation and to reach quantitative H2 yields. The technique also was optimized to provide acceptable sample throughput. Results The classical HTC reaction of a number of selected compounds exhibited H2 yields from 60 to 90 %. Yields close to 100 % were measured for the experiments with the chromium-enhanced reactor. The δ2H values also were substantially different between the two types of experiments. For the majority of the compounds studied, a highly significant relationship was observed between the amount of missing H2and the number of nitrogen atoms in the molecules, suggesting the pyrolytic formation of HCN as a byproduct. A similar linear relationship was found between the amount of missing H2 and the observed hydrogen isotopic result, reflecting isotopic fractionation. Conclusions The classical HTC technique to produce H2 from organic materials using high temperatures in the presence of glassy carbon is not suitable for nitrogen-bearing compounds. Adding chromium to the reaction zone improves the yield to 100 % in most cases. The initial formation of HCN is accompanied by a strong hydrogen isotope effect, with the observed hydrogen isotope results on H2 being substantially shifted to more negative δ2H values. The reaction can be understood as an initial disproportionation leading to H2 and HCN

  12. Simultaneous Analysis of Nitrogen, Carbon and Sulfur Stable Isotopes and Concentrations in Organics and Soils

    NASA Astrophysics Data System (ADS)

    Mambelli, S.; Brooks, P. D.; Sutka, R.; Hughes, S.; Finstad, K. M.; Pakes, M. J.; Dawson, T. E.

    2014-12-01

    To date, analysis of diet, food web complexities, biogeochemical cycles, and ecosystem functioning have largely focused on using variation in carbon (C) and nitrogen (N) stable isotope ratios. This is because a great deal is understood about what leads to this variation and because the dual stable isotope analysis of these two elements using continuous flow isotope ratio mass spectrometry (IRMS) is now commonplace. However, the aforementioned studies may all greatly benefit from the additional information one can get from also having sulfur (S) stable isotopes ratio data. Until very recently the analysis of δ34S has traditionally required an additional and often more difficult analytical procedure. Here, we report on the development of a new method that simultaneously analyzes the elemental and isotopic composition of N, C and S in a single sample. The new commercially available instrument includes a modified NCS elemental analyzer in line with an IRMS outfitted with 100 volt AD converters for wide dynamic range. We tested, and modified, this instrument to achieve maximum accuracy and precision for the isotopic measurements of all three elements. We found that the original design needed improvements to achieve our goals by: a) including a component (originally designed for trapping water) as buffer to reduce S memory and obtain reliable δ34S analysis; b) adding an external furnace for complete reduction of nitrogen oxides to N2 gas for accurate δ15N; c) adding a magnesium perchlorate water trap immediately after the reduction tube to minimize any water condensation that could also influence S memory. We analyzed a selection of organic materials and soils with approximately a 1:2 standards versus unknowns ratio per run. Using this NCS set-up, the precision of the N and C isotopic measurements was comparable to the one usually attained in NC mode alone (standard deviation of ± 0.13 δ15N in the range 30 to 400 µg N, and of ± 0.12 δ13C in the range 0.20 to 4 mg

  13. Compound-specific carbon, nitrogen, and hydrogen isotope analysis of N-nitrosodimethylamine in aqueous solutions.

    PubMed

    Spahr, Stephanie; Bolotin, Jakov; Schleucher, Jürgen; Ehlers, Ina; von Gunten, Urs; Hofstetter, Thomas B

    2015-03-01

    Mitigation of N-nitrosodimethylamine (NDMA) and other hazardous water disinfection byproducts (DBP) is currently hampered by a limited understanding of DBP formation mechanisms. Because variations of the stable isotope composition of NDMA can potentially reveal reaction pathways and precursor compounds, we developed a method for the compound-specific isotope analysis (CSIA) of (13)C/(12)C, (15)N/(14)N, and (2)H/(1)H ratios of NDMA by gas chromatography coupled to isotope ratio mass spectrometry (GC/IRMS). Method quantification limits for the accurate isotope analysis of NDMA, N-nitrosodiethyl-, -dipropyl-, and -dibutylamine as well as N-nitrosopyrrolidine were between 0.18 to 0.60 nmol C, 0.40 to 0.80 nmol N, and 2.2 to 5.8 nmol H injected on column. Coupling solid phase extraction (SPE) to GC/IRMS enabled the precise quantification of C, N, and H isotope ratios of NDMA in aqueous samples at concentrations of 0.6 μM (45 μg L(-1)). We validated the proposed method with a laboratory experiment, in which NDMA was formed with stoichiometric yield (97 ± 4%) through chloramination of the pharmaceutical ranitidine (3 μM). δ(13)C and δ(2)H values of NDMA remained constant during NDMA formation while its δ(15)N increased due to a reaction at a N atom in the rate-limiting step of NDMA formation. The δ(2)H value of NDMA determined by SPE-GC/IRMS also corresponded well to the δ(2)H value of the N(CH3)2-group of ranitidine measured by quantitative deuterium nuclear magnetic resonance spectroscopy. This observation implies that the N(CH3)2-moiety of ranitidine is transferred to NDMA without being chemically altered and illustrates the accuracy of the proposed method.

  14. Demonstration of compound-specific isotope analysis of hydrogen isotope ratios in chlorinated ethenes.

    PubMed

    Kuder, Tomasz; Philp, Paul

    2013-02-01

    High-temperature pyrolysis conversion of organic analytes to H(2) in hydrogen isotope ratio compound-specific isotope analysis (CSIA) is unsuitable for chlorinated compounds such as trichloroethene (TCE) and cis-1,2-dichloroethene (DCE), due to competition from HCl formation. For this reason, the information potential of hydrogen isotope ratios of chlorinated ethenes remains untapped. We present a demonstration of an alternative approach where chlorinated analytes reacted with chromium metal to form H(2) and minor amounts of HCl. The values of δ(2)H were obtained at satisfactory precision (± 10 to 15 per thousand), however the raw data required daily calibration by TCE and/or DCE standards to correct for analytical bias that varies over time. The chromium reactor has been incorporated into a purge and trap-CSIA method that is suitable for CSIA of aqueous environmental samples. A sample data set was obtained for six specimens of commercial product TCE. The resulting values of δ(2)H were between -184 and +682 ‰, which significantly widened the range of manufactured TCE δ(2)H signatures identified by past work. The implications of this finding to the assessment of TCE contamination are discussed.

  15. An accurate, convective energy equation based automated meshing technique for analysis of blood vessels and tissues.

    PubMed

    White, J A; Dutton, A W; Schmidt, J A; Roemer, R B

    2000-01-01

    An automated three-element meshing method for generating finite element based models for the accurate thermal analysis of blood vessels imbedded in tissue has been developed and evaluated. The meshing method places eight noded hexahedral elements inside the vessels where advective flows exist, and four noded tetrahedral elements in the surrounding tissue. The higher order hexahedrals are used where advective flow fields occur, since high accuracy is required and effective upwinding algorithms exist. Tetrahedral elements are placed in the remaining tissue region, since they are computationally more efficient and existing automatic tetrahedral mesh generators can be used. Five noded pyramid elements connect the hexahedrals and tetrahedrals. A convective energy equation (CEE) based finite element algorithm solves for the temperature distributions in the flowing blood, while a finite element formulation of a generalized conduction equation is used in the surrounding tissue. Use of the CEE allows accurate solutions to be obtained without the necessity of assuming ad hoc values for heat transfer coefficients. Comparisons of the predictions of the three-element model to analytical solutions show that the three-element model accurately simulates temperature fields. Energy balance checks show that the three-element model has small, acceptable errors. In summary, this method provides an accurate, automatic finite element gridding procedure for thermal analysis of irregularly shaped tissue regions that contain important blood vessels. At present, the models so generated are relatively large (in order to obtain accurate results) and are, thus, best used for providing accurate reference values for checking other approximate formulations to complicated, conjugated blood heat transfer problems.

  16. Tools for Accurate and Efficient Analysis of Complex Evolutionary Mechanisms in Microbial Genomes. Final Report

    SciTech Connect

    Nakhleh, Luay

    2014-03-12

    I proposed to develop computationally efficient tools for accurate detection and reconstruction of microbes' complex evolutionary mechanisms, thus enabling rapid and accurate annotation, analysis and understanding of their genomes. To achieve this goal, I proposed to address three aspects. (1) Mathematical modeling. A major challenge facing the accurate detection of HGT is that of distinguishing between these two events on the one hand and other events that have similar "effects." I proposed to develop a novel mathematical approach for distinguishing among these events. Further, I proposed to develop a set of novel optimization criteria for the evolutionary analysis of microbial genomes in the presence of these complex evolutionary events. (2) Algorithm design. In this aspect of the project, I proposed to develop an array of e cient and accurate algorithms for analyzing microbial genomes based on the formulated optimization criteria. Further, I proposed to test the viability of the criteria and the accuracy of the algorithms in an experimental setting using both synthetic as well as biological data. (3) Software development. I proposed the nal outcome to be a suite of software tools which implements the mathematical models as well as the algorithms developed.

  17. High-Precision Selenium Isotope Analysis by Hydride Generation MC-ICP-MS: Environmental Applications

    NASA Astrophysics Data System (ADS)

    Schmidberger, S.; Simonetti, A.; Gariépy, C.

    2003-04-01

    The global cycle and the natural isotopic variation of Se in the lithosphere, biosphere, hydrosphere and atmosphere are currently little constrained. The study of Se isotope systematics by negative thermal ionization mass spectrometry (NTIMS) has documented large Se isotope variations up to 15 ppm in various natural samples (δ80Se/76Se; Johnson et al., 1999), indicating its important potential as a tracer in geological and biological processes. Recently, Se isotope measurements on sulfide deposits from hydrothermal systems were obtained using a Micromass IsoProbe multicollector inductively coupled plasma mass spectrometer coupled to a hydride generator (Rouxel et al. 2002). This technique allows for high-precision Se isotope analysis on small sample sizes (<= 100 ng), and thus is a prerequisite for precise Se isotope measurements in low abundance samples such as precipitations, freshwaters and atmospheric aerosols (1 ppb or less). We have developed a 74-82Se double spike technique, which corrects for instrumental mass fractionation during both isotopic analysis and chemical processing. During double spike calibration, mass discrimination was monitored using a Germanium Specpuretextregistered standard (25 ppb). The isotopic composition of the Ge standard was accurately determined using a 10 ppb solution of the isotopic Gallium standard SRM 994. Repeated measurements (n=8) of the Ge standard yielded an external reproducibility of 0.13 ppm and a 74Ge/72Ge ratio of 1.32987. Instrumental mass bias evaluated with the Ge standard was essentially invariant over a three-month period. Our results yield an external reproducibility of 0.4 ppm (80Se/76Se) for a 100 ppb solution of the Se standard SRM 3149 (˜100 ng of total Se consumed). This ongoing study focuses on determining the Se isotopic compositions of precipitations and aerosol samples from remote and urban areas in northeastern North America. The preliminary results for precipitation samples (˜100 to 300 ml of rain

  18. On-site isotopic analysis of dissolved inorganic carbon using an isotope ratio infrared spectrometer

    NASA Astrophysics Data System (ADS)

    Stoltmann, Tim; Mandic, Magda; Stöbener, Nils; Wapelhorst, Eric; Aepfler, Rebecca; Hinrichs, Kai-Uwe; Taubner, Heidi; Jost, Hj; Elvert, Marcus

    2016-04-01

    An Isotope Ratio Infrared Spectrometer (IRIS) has been adapted to perform measurements of δ13C of dissolved inorganic carbon (DIC) in marine pore waters. The resulting prototype allowed highly automated analysis of δ13C isotopic ratios and CO2 concentration. We achieved a throughput of up to 70 samples per day with DIC contents as low as 1.7 μmol C. We achieved an internal precision of 0.066 ‰ and an external precision of 0.16 ‰, which is comparable to values given for Isotope Ratio Mass Spectrometers (IRMS). The prototype instrument is field deployable, suitable for shipboard analysis of deep sea core pore waters. However, the validation of the prototype was centered around a field campaign in Eckernförde Bay, NW- Baltic Sea. As a proof of concept, a shallow site within an area of submarine groundwater discharge (SGD) and a site outside this area was investigated. We present profiles of δ13C of DIC over 50 cm exhibiting well understood methane turnover processes (anaerobic oxidation of methane). At the lowest point below the seafloor, microbial reduction of CO2 to CH4 dominates. 12CO2 is reduced preferentially over 13CO2, leading to more positive δ13C values in the remaining DIC pool; in layers closer to the surface, the oxidation of CH4 to CO2 becomes more prominent. Since the CH4 pool is enriched in 12C a shift to more negative δ13C can be observed in the DIC pool. In the upper 15 cm, the pore water DIC mixes with the sea water DIC, increasing δ13C again. Finally, we will present recent developments to further improve performance and future plans for deployments on research cruises.

  19. On-site isotopic analysis of dissolved inorganic carbon using an isotope ratio infrared spectrometer

    NASA Astrophysics Data System (ADS)

    Jost, H. J. H.; Stoltmann, T.; Stöbener, N.; Wapelhorst, E.; Mandic, M.; Aepfler, R.; Hinrichs, K. U.; Taubner, H.; Elvert, M.

    2015-12-01

    An Isotope Ratio Infrared Spectrometer (IRIS) has been adapted to perform measurements of δ13C of dissolved inorganic carbon (DIC) in marine pore waters. The resulting prototype allowed highly automated analysis of δ13C isotopic ratios and CO2 concentration. We achieved a throughput of up to 70 samples per day with DIC contents as low as 1.7 μmol C. We achieved an internal precision of 0.066 ‰ and an external precision of 0.16 ‰, which is comparable to values given for Isotope Ratio Mass Spectrometers (IRMS). The prototype instrument is field deployable, suitable for shipboard analysis of deep sea core pore waters. However, the validation of the prototype was centered around a field campaign in Eckernförde Bay, NW- Baltic Sea. As a proof of concept, a shallow site within an area of submarine groundwater discharge (SGD) and a site outside this area was investigated. We present profiles of δ13C of DIC over 50 cm exhibiting well understood methane turnover processes (anaerobic oxidation of methane). At the lowest point below the seafloor, microbial reduction of CO2 to CH4 dominates. 12CO2 is reduced preferentially over 13CO2, leading to more positive δ13C values in the remaining DIC pool; in layers closer to the surface, the oxidation of CH4 to CO2 becomes more prominent. Since the CH4 pool is enriched in 12C a shift to more negative δ13C can be observed in the DIC pool. In the upper 15 cm, the pore water DIC mixes with the sea water DIC, increasing δ13C again. Finally, we will present recent developments to further improve performance and future plans for deployments on research cruises.

  20. Least destructive sampling of human remains using laser drilling for Sr isotope analysis by TIMS

    NASA Astrophysics Data System (ADS)

    Willmes, Malte; Moffat, Ian; Grün, Rainer; Armstrong, Richard; Kinsley, Les; McMorrow, Linda

    2013-04-01

    Strontium isotope ratios (87Sr/86Sr) measured in ancient human remains can be used to reconstruct migration patterns of ancient human populations. This application is based on the fact that different geologic regions have distinct Sr isotope signatures that are cycled through the soils, plants and rivers, and eventually enter the food cycle. Sr isotope ratios measured in skeletal remains (bones and teeth) reflect the average of dietary Sr that was consumed when the tissue was formed, allowing the investigation of human migration between geologically distinct terrains. The analysis of human remains is always a sensitive topic requiring minimal damage to the sample, while at the same time providing highly precise and accurate results. Samples can be analysed either by solution methods like thermal ionisation mass spectrometry (TIMS), or by in-situ laser ablation MC-ICP-MS. For TIMS a drill is used to extract a small amount of sample, which is then digested in acid and Sr is separated out using ion exchange chromatography. This technique provides highly precise and accurate results, because any isobaric interferences are removed during chemical separation. The drawback is that drilling may cause visible damage to the sample, restricting access to precious human remains. LA-MC-ICP-MS analysis is very fast and nearly destruction free. However, the accuracy and precision of LA-MC-ICP-MS is limited by a number of factors including large instrumental mass discrimination, laser-induced isotopic and elemental fractionations and molecular interferences on 87Sr. Its application thus requires rigorous data reduction, which can introduce significant uncertainties into the analysis. This is especially true for samples with relatively low Sr concentrations such as human teeth (e.g., Woodhead et al., 2005; Horstwood et al., 2008; Vroon et al., 2008). In addition, LA-MC-ICP-MS has traditionally required a flat sample surface, thus an unbroken tooth needs to be cut, which is rather

  1. Automated SIMS Isotopic Analysis Of Small Dust Particles

    NASA Astrophysics Data System (ADS)

    Nittler, L.; Alexander, C.; Gyngard, F.; Morgand, A.; Zinner, E. K.

    2009-12-01

    The isotopic compositions of sub-μm to μm sized dust grains are of increasing interest in cosmochemistry, nuclear forensics and terrestrial aerosol research. Because of its high sensitivity and spatial resolution, Secondary Ion Mass Spectrometry (SIMS) is the tool of choice for measuring isotopes in such small samples. Indeed, SIMS has enabled an entirely new sub-field of astronomy: presolar grains in meteorites. In recent years, the development of the Cameca NanoSIMS ion probe has extended the reach of isotopic measurements to particles as small as 100 nm in diameter, a regime where isotopic precision is strongly limited by the total number of atoms in the sample. Many applications require obtaining isotopic data on large numbers of particles, necessitating the development of automated techniques. One such method is isotopic imaging, wherein images of multiple isotopes are acquired, each containing multiple dispersed particles, and image processing is used to determine isotopic ratios for individual particles. This method is powerful, but relatively inefficient for raster-based imaging on the NanoSIMS. Modern computerized control of instrumentation has allowed for another approach, analogous to commercial automated SEM-EDS particle analysis systems, in which images are used solely to locate particles followed by fully automated grain-by-grain analysis. The first such system was developed on the Carnegie Institution’s Cameca ims-6f, and was used to generate large databases of presolar grains. We have recently developed a similar system for the NanoSIMS, whose high sensitivity allows for smaller grains to be analyzed with less sample consumption than is possible with the 6f system. The 6f and NanoSIMS systems are functionally identical: an image of dispersed grains is obtained with sufficient statistical precision for an algorithm to identify the positions of individual particles, the primary ion beam is deflected to each particle in turn and rastered in a small

  2. Gravitational waves from compact binaries inspiralling along post-Newtonian accurate eccentric orbits: Data analysis implications

    SciTech Connect

    Tessmer, Manuel; Gopakumar, Achamveedu

    2008-10-15

    Compact binaries inspiralling along eccentric orbits are plausible gravitational-wave (GW) sources for the ground-based laser interferometers. We explore the losses in the event rates incurred when searching for GWs from compact binaries inspiralling along post-Newtonian accurate eccentric orbits with certain obvious nonoptimal search templates. For the present analysis, GW signals having 2.5 post-Newtonian (PN) accurate orbital evolution are modeled following the phasing formalism, presented by T. Damour, A. Gopakumar, and B. R. Iyer [Phys. Rev. D 70, 064028 (2004)]. We demonstrate that the search templates that model in a gauge-invariant manner GWs from compact binaries inspiralling under quadrupolar radiation reaction along 2PN accurate circular orbits are very efficient in capturing our somewhat realistic GW signals. However, three types of search templates based on the adiabatic, complete adiabatic, and gauge-dependent complete nonadiabatic approximants, detailed in P. Ajith, B. R. Iyer, C. A. K. Robinson, and B. S. Sathyaprakash, Phys. Rev. D 71, 044029 (2005), relevant for the circular inspiral under the quadrupolar radiation reaction were found to be inefficient in capturing the above-mentioned eccentric signal. We conclude that further investigations will be required to probe the ability of various types of PN accurate circular templates, employed to analyze the LIGO/VIRGO data, to capture GWs from compact binaries having tiny orbital eccentricities.

  3. Gravitational waves from compact binaries inspiralling along post-Newtonian accurate eccentric orbits: Data analysis implications

    NASA Astrophysics Data System (ADS)

    Tessmer, Manuel; Gopakumar, Achamveedu

    2008-10-01

    Compact binaries inspiralling along eccentric orbits are plausible gravitational-wave (GW) sources for the ground-based laser interferometers. We explore the losses in the event rates incurred when searching for GWs from compact binaries inspiralling along post-Newtonian accurate eccentric orbits with certain obvious nonoptimal search templates. For the present analysis, GW signals having 2.5 post-Newtonian (PN) accurate orbital evolution are modeled following the phasing formalism, presented by T. Damour, A. Gopakumar, and B. R. Iyer [Phys. Rev. D 70, 064028 (2004)PRVDAQ0556-282110.1103/PhysRevD.70.064028]. We demonstrate that the search templates that model in a gauge-invariant manner GWs from compact binaries inspiralling under quadrupolar radiation reaction along 2PN accurate circular orbits are very efficient in capturing our somewhat realistic GW signals. However, three types of search templates based on the adiabatic, complete adiabatic, and gauge-dependent complete nonadiabatic approximants, detailed in P. Ajith, B. R. Iyer, C. A. K. Robinson, and B. S. Sathyaprakash, Phys. Rev. D 71, 044029 (2005)PRVDAQ0556-282110.1103/PhysRevD.71.044029, relevant for the circular inspiral under the quadrupolar radiation reaction were found to be inefficient in capturing the above-mentioned eccentric signal. We conclude that further investigations will be required to probe the ability of various types of PN accurate circular templates, employed to analyze the LIGO/VIRGO data, to capture GWs from compact binaries having tiny orbital eccentricities.

  4. Carbon isotopic analysis of atmospheric methane by isotope-ratio-monitoring gas chromatography-mass spectrometry

    NASA Technical Reports Server (NTRS)

    Merritt, Dawn A.; Hayes, J. M.; Des Marais, David J.

    1995-01-01

    Less than 15 min are required for the determination of delta C(sub PDB)-13 with a precision of 0.2 ppt(1 sigma, single measurement) in 5-mL samples of air containing CH4 at natural levels (1.7 ppm). An analytical system including a sample-introduction unit incorporating a preparative gas chromatograph (GC) column for separation of CH4 from N2, O2, and Ar is described. The 15-min procedure includes time for operation of that system, high-resolution chromatographic separation of the CH4, on-line combustion and purification of the products, and isotopic calibration. Analyses of standards demonstrate that systematic errors are absent and that there is no dependence of observed values of delta on sample size. For samples containing 100 ppm or more CH4, preconcentration is not required and the analysis time is less than 5 min. The system utilizes a commercially available, high-sensitivity isotope-ratio mass spectrometer. For optimal conditions of smaple handling and combustion, performance of the system is within a factor of 2 of the shot-noise limit. The potential exists therefore for analysis of samples as small as 15 pmol CH4 with a standard deviation of less than 1 ppt.

  5. A Global Approach to Accurate and Automatic Quantitative Analysis of NMR Spectra by Complex Least-Squares Curve Fitting

    NASA Astrophysics Data System (ADS)

    Martin, Y. L.

    The performance of quantitative analysis of 1D NMR spectra depends greatly on the choice of the NMR signal model. Complex least-squares analysis is well suited for optimizing the quantitative determination of spectra containing a limited number of signals (<30) obtained under satisfactory conditions of signal-to-noise ratio (>20). From a general point of view it is concluded, on the basis of mathematical considerations and numerical simulations, that, in the absence of truncation of the free-induction decay, complex least-squares curve fitting either in the time or in the frequency domain and linear-prediction methods are in fact nearly equivalent and give identical results. However, in the situation considered, complex least-squares analysis in the frequency domain is more flexible since it enables the quality of convergence to be appraised at every resonance position. An efficient data-processing strategy has been developed which makes use of an approximate conjugate-gradient algorithm. All spectral parameters (frequency, damping factors, amplitudes, phases, initial delay associated with intensity, and phase parameters of a baseline correction) are simultaneously managed in an integrated approach which is fully automatable. The behavior of the error as a function of the signal-to-noise ratio is theoretically estimated, and the influence of apodization is discussed. The least-squares curve fitting is theoretically proved to be the most accurate approach for quantitative analysis of 1D NMR data acquired with reasonable signal-to-noise ratio. The method enables complex spectral residuals to be sorted out. These residuals, which can be cumulated thanks to the possibility of correcting for frequency shifts and phase errors, extract systematic components, such as isotopic satellite lines, and characterize the shape and the intensity of the spectral distortion with respect to the Lorentzian model. This distortion is shown to be nearly independent of the chemical species

  6. Hanford Isotope Project strategic business analysis Cesium-137 (Cs-137)

    SciTech Connect

    1995-10-01

    The purpose of this business analysis is to address the beneficial reuse of Cesium 137 (Cs-137) in order to utilize a valuable national asset and possibly save millions of tax dollars. Food irradiation is the front runner application along with other uses. This business analysis supports the objectives of the Department of Energy National Isotope Strategy distributed in August 1994 which describes the DOE plans for the production and distribution of isotope products and services. As part of the Department`s mission as stated in that document. ``The Department of Energy will also continue to produce and distribute other radioisotopes and enriched stable isotopes for medical diagnostics and therapeutics, industrial, agricultural, and other useful applications on a businesslike basis. This is consistent with the goals and objectives of the National Performance Review. The Department will endeavor to look at opportunities for private sector to co-fund or invest in new ventures. Also, the Department will seek to divest from ventures that can more profitably or reliably be operated by the private sector.``

  7. Accurate near-field calculation in the rigorous coupled-wave analysis method

    NASA Astrophysics Data System (ADS)

    Weismann, Martin; Gallagher, Dominic F. G.; Panoiu, Nicolae C.

    2015-12-01

    The rigorous coupled-wave analysis (RCWA) is one of the most successful and widely used methods for modeling periodic optical structures. It yields fast convergence of the electromagnetic far-field and has been adapted to model various optical devices and wave configurations. In this article, we investigate the accuracy with which the electromagnetic near-field can be calculated by using RCWA and explain the observed slow convergence and numerical artifacts from which it suffers, namely unphysical oscillations at material boundaries due to the Gibbs phenomenon. In order to alleviate these shortcomings, we also introduce a mathematical formulation for accurate near-field calculation in RCWA, for one- and two-dimensional straight and slanted diffraction gratings. This accurate near-field computational approach is tested and evaluated for several representative test-structures and configurations in order to illustrate the advantages provided by the proposed modified formulation of the RCWA.

  8. Evaluation of automated threshold selection methods for accurately sizing microscopic fluorescent cells by image analysis.

    PubMed Central

    Sieracki, M E; Reichenbach, S E; Webb, K L

    1989-01-01

    The accurate measurement of bacterial and protistan cell biomass is necessary for understanding their population and trophic dynamics in nature. Direct measurement of fluorescently stained cells is often the method of choice. The tedium of making such measurements visually on the large numbers of cells required has prompted the use of automatic image analysis for this purpose. Accurate measurements by image analysis require an accurate, reliable method of segmenting the image, that is, distinguishing the brightly fluorescing cells from a dark background. This is commonly done by visually choosing a threshold intensity value which most closely coincides with the outline of the cells as perceived by the operator. Ideally, an automated method based on the cell image characteristics should be used. Since the optical nature of edges in images of light-emitting, microscopic fluorescent objects is different from that of images generated by transmitted or reflected light, it seemed that automatic segmentation of such images may require special considerations. We tested nine automated threshold selection methods using standard fluorescent microspheres ranging in size and fluorescence intensity and fluorochrome-stained samples of cells from cultures of cyanobacteria, flagellates, and ciliates. The methods included several variations based on the maximum intensity gradient of the sphere profile (first derivative), the minimum in the second derivative of the sphere profile, the minimum of the image histogram, and the midpoint intensity. Our results indicated that thresholds determined visually and by first-derivative methods tended to overestimate the threshold, causing an underestimation of microsphere size. The method based on the minimum of the second derivative of the profile yielded the most accurate area estimates for spheres of different sizes and brightnesses and for four of the five cell types tested. A simple model of the optical properties of fluorescing objects and

  9. ATTA - A New Method of Ultrasensitive Trace-Isotope Analysis

    NASA Astrophysics Data System (ADS)

    Lu, Z.-T.; Bailey, K.; Chen, C. Y.; Du, X.; Li, Y. M.; O'Connor, T. P.; Young, L.; Winkler, G.

    2000-10-01

    We have developed a new method of ultrasensitive trace-isotope analysis based upon the technique of laser manipulation of neutral atoms [1]. This new method allows us to count individual 85Kr and 81Kr atoms present in a natural krypton sample with isotopic abundances in the range of 10-11 and 10-13, respectively. Isotope analysis of 81Kr can be used to date polar ice, and 85Kr is a tracer used in monitoring nuclear wastes. In this experiment metastable Kr atoms were produced in a discharge, decelerated via the Zeeman slowing technique, and captured by a Magneto-Optical Trap where the atoms were counted by measuring their fluorescence. At present our system is capable of counting, in average, one 81Kr atom for about 12 minutes with a total efficiency of 2x10-7. We are currently working to improve our system efficiency by applying cryogenic cooling to the Kr atoms in the discharge region and by recirculating the gas in the vacuum system. This method can be used to analyze many other isotope tracers for a wide range of applications including measuring solar neutrino flux, searching for exotic particles, tracing atmospheric and oceanic currents, archeological and geological dating, medical diagnostics, monitoring fission products in the environment for nuclear waste management, etc. This work is supported by the U.S. Department of Energy, Nuclear Physics Division; L.Young is supported by the Office of Basic Energy Sciences, Division of Chemical Sciences (Contract W-31-109-ENG-38). [1] C.Y. Chen et. al., Science 286, 1139 (1999).

  10. Full Range MGA Plutonium Isotopic Analysis using Single Ge Detector

    SciTech Connect

    Buckley, W.M.; Wang, T.F.; Friensehner, A.; Kreek, S.A.; Lanier, R.G.; Parker, W.E.; Ruhter, W.; Twomey, T.; Martinez, D.; Keyser, R.; Sangsingkeow, P.

    2000-06-26

    The Gamma-Ray multi-group analysis code MGA developed at Lawrence Livermore National Laboratory has been widely used in the area of gamma-ray non-destructive plutonium assay. This plutonium isotopic analysis code de-convolutes the complicated, 100-keV x-ray and gamma-ray region to obtain the ratio of Pu isotopes. Calibration of the detector efficiency is not required, but is determined intrinsically from the measured spectra. The code can either analyze low-energy gamma-ray spectrum taken using a high-resolution HPGe detector for energies below 300 keV, or analyze the low-energy spectrum combined with a high-energy spectrum (up to 1 MeV) in the two-detector analysis mode. In the latter case, the use of two detectors has been mandated by the conflicting requirements: excellent resolution at low energies (characteristic of small planar detectors) with good high-energy efficiency (characteristic of coaxial detectors). Usually, a high-energy spectrum taken using a coaxial Ge detector will not provide sufficient energy resolution for 100-keV plutonium isotopic analysis, while the small planar used at low energies has inadequate high-energy efficiency. An optimized-geometry ORTEC HPGe detector has been developed which combines good energy resolution at 100 keV combined with acceptable high-energy ({approx} 1 MeV) efficiency in a single detector. It has been used to gather spectra of both low- and high-energy regions of plutonium spectra simultaneously, for analysis by MGA in the two-detector mode. Five Pu gamma-ray calibration standard sources were used in this study of this special detector.

  11. A new method of tree xylem water extraction for isotopic analysis

    NASA Astrophysics Data System (ADS)

    Gierke, C.; Newton, B. T.

    2011-12-01

    The Sacramento Mountain Watershed Study in the southern Sacramento Mountains of New Mexico is designed to assess the forest restoration technique of tree thinning in mountain watersheds as an effective method of increasing local and regional groundwater recharge. The project is using a soil water balance approach to quantify the partitioning of local precipitation within this watershed before and after thinning trees. Understanding what sources trees extract their water from (e.g. shallow groundwater, unsaturated fractured bedrock, and soils) is difficult due to a complex hydrologic system and heterogeneous distribution of soil thicknesses. However, in order to accurately quantify the soil water balance and to assess how thinning trees will affect this water balance, it is important determine the sources from which trees extract their water. We plan to use oxygen and hydrogen stable isotopic analysis of various end member waters to identify these different sources. We are in the process of developing a new method of determining the isotopic composition of tree water that has several advantages over conventional methods. Within the tree there is the xylem which transports water from the roots to the leaves and the phloem which transports starches and sugars in a water media throughout the tree. Previous studies have shown that the isotopic composition of xylem water accurately reflects that of source water, while phloem water has undergone isotopic fractionation during photosynthesis and metabolism. The distillation of water from twigs, which is often used to extract tree water for isotopic analysis, is very labor intensive. Other disadvantages to distillation methods include possible fractionation due to phase changes and the possible extraction of fractionated phloem waters. Employing a new mixing method, the composition of the twig water (TW) can be determined by putting twigs of unknown isotopic water composition into waters of known compositions or initial

  12. Accurate analysis of blood vessel sizes and stenotic lesions using stereoscopic DSA system.

    PubMed

    Fencil, L E; Doi, K; Hoffman, K R

    1988-01-01

    We have developed a technique to determine accurately the magnification factor and three-dimensional orientation of a vessel segment from a stereoscopic pair of digital subtraction angiograms (DSA). Our DSA system includes a stereoscopic x-ray tube with a 25-mm focal spot shift. The magnification and orientation of a selected vessel segment are determined from the distance and direction of the focal spot shift and the stereoscopic discrepancy in image positions for that segment. Our results indicate that the accuracies of determining the magnification and orientation are less than 1% and approximately 5 degrees, respectively. After the magnification and orientation are determined accurately, an iterative deconvolution technique for the measurement of vessel image size is applied to the selected vessel segment. This iterative deconvolution technique provides the best estimate of vessel image size by taking into account the unsharpness of the digital system. With this technique, the vessel image size can be determined to an accuracy of approximately 1.0 mm, which corresponds to one third the pixel size of our DSA system. Information derived from stereoscopic analysis and iterative deconvolution thus allows accurate calculation of actual vascular dimensions from DSA images.

  13. Characterization of phenols biodegradation by compound specific stable isotope analysis

    NASA Astrophysics Data System (ADS)

    Wei, Xi; Gilevska, Tetyana; Wenzig, Felix; Hans, Richnow; Vogt, Carsten

    2015-04-01

    -cresol degradation and 2.2±0.3‰ for m-cresol degradation, respectively. The carbon isotope fractionation patterns of phenol degradation differed more profoundly. Oxygen-dependent monooxygenation of phenol by A.calcoaceticus as the initial reaction yielded ƐC values of -1.5±0.02‰. In contrast, the anaerobic degradation initiated by ATP-dependent carboxylation performed by Thauera aromatia DSM 6984, produced no detectable fractionation (ƐC 0±0.1‰). D. cetonica showed a slight inverse carbon isotope fractionation (ƐC 0.4±0.1‰). In conclusion, a validated method for compound specific stable isotope analysis was developed for phenolic compounds, and the first data set of carbon enrichment factors upon the biodegradation of phenol and cresols with different activation mechanisms has been obtained in the present study. Carbon isotope fractionation analysis is a potentially powerful tool to monitor phenolic compounds degradation in the environment.

  14. Isotopic analysis for degradation diagnosis of calcite matrix in mortar.

    PubMed

    Dotsika, E; Psomiadis, D; Poutoukis, D; Raco, B; Gamaletsos, P

    2009-12-01

    Mortar that was used in building as well as in conservation and restoration works of wall paintings have been analysed isotopically (delta(13)C and delta(18)O) in order to evaluate the setting environments and secondary processes, to distinguish the structural components used and to determine the exact causes that incurred the degradation phenomena. The material undergoes weathering and decay on a large proportion of its surface and in depth, due to the infiltration of water through the structural blocks. Mineralogical analysis indicated signs of sulphation and dissolution/recrystallisation processes taking place on the material, whereas stable isotopes provided information relative to the origin of the CO(2) and water during calcite formation and degradation processes. Isotopic change of the initial delta(13)C and delta(18)O in carbonate matrix was caused by alteration of the primary source of CO(2) and H(2)O in mortar over time, particularly by recrystallisation of calcite with porewater, evaporated or re-condensed water, and CO(2) from various sources of atmospheric and biogenic origin. Human influence (surface treatment) and biological growth (e.g. fungus) are major exogenic processes which may alter delta(18)O and delta(13)C in lime mortar.

  15. Nonlinear Aeroelastic Analysis Using a Time-Accurate Navier-Stokes Equations Solver

    NASA Technical Reports Server (NTRS)

    Kuruvila, Geojoe; Bartels, Robert E.; Hong, Moeljo S.; Bhatia, G.

    2007-01-01

    A method to simulate limit cycle oscillation (LCO) due to control surface freeplay using a modified CFL3D, a time-accurate Navier-Stokes computational fluid dynamics (CFD) analysis code with structural modeling capability, is presented. This approach can be used to analyze aeroelastic response of aircraft with structural behavior characterized by nonlinearity in the force verses displacement curve. A limited validation of the method, using very low Mach number experimental data for a three-degrees-of-freedom (pitch/plunge/flap deflection) airfoil model with flap freeplay, is also presented.

  16. Enantiomeric and Isotopic Analysis of Sugar Derivatives in Carbonaceous Meteorites

    NASA Technical Reports Server (NTRS)

    Cooper, George; Asiyo, Cynthia; Turk, Kendra; DeVincenzi, Donald (Technical Monitor)

    2002-01-01

    Several classes of organic compounds are found in carbonaceous meteorites including amino acids, carboxylic acids, hydroxy acids, purines, and pyrimidines. Such compounds are thought to have been delivered to the early Earth in asteroids and comets and may have played a role in the origin of life. Likewise, sugar derivatives are critical to all known lifeforms. Recent analyses of the Murchison and Murray carbonaceous meteorites revealed a diverse suite of such derivatives, i.e., sugar alcohols, and sugar acids. This presentation will focus primarily on the analysis of individual sugar acids - their enantiomeric and isotopic composition. Analysis of these compounds may reveal the nature of past (or present) meteoritic sugars themselves. For example, if parent sugars decomposed (by well-known mechanisms) to give the present acids, were their enantiomeric ratios preserved? Combined with other evidence, the enantiomeric composition of such compounds as glyceric acid and (especially) rare acids may help to answer such questions. C-13 and D isotope analysis of meteoritic sugar alcohols (glycerol, threitol, ribitol, etc.) as a group revealed that they were indigenous to the meteorite. Preliminary C-13 analysis of glyceric acid shows that it is also extraterrestrial.

  17. Monte Carlo isotopic inventory analysis for complex nuclear systems

    NASA Astrophysics Data System (ADS)

    Phruksarojanakun, Phiphat

    Monte Carlo Inventory Simulation Engine (MCise) is a newly developed method for calculating isotopic inventory of materials. It offers the promise of modeling materials with complex processes and irradiation histories, which pose challenges for current, deterministic tools, and has strong analogies to Monte Carlo (MC) neutral particle transport. The analog method, including considerations for simple, complex and loop flows, is fully developed. In addition, six variance reduction tools provide unique capabilities of MCise to improve statistical precision of MC simulations. Forced Reaction forces an atom to undergo a desired number of reactions in a given irradiation environment. Biased Reaction Branching primarily focuses on improving statistical results of the isotopes that are produced from rare reaction pathways. Biased Source Sampling aims at increasing frequencies of sampling rare initial isotopes as the starting particles. Reaction Path Splitting increases the population by splitting the atom at each reaction point, creating one new atom for each decay or transmutation product. Delta Tracking is recommended for high-frequency pulsing to reduce the computing time. Lastly, Weight Window is introduced as a strategy to decrease large deviations of weight due to the uses of variance reduction techniques. A figure of merit is necessary to compare the efficiency of different variance reduction techniques. A number of possibilities for figure of merit are explored, two of which are robust and subsequently used. One is based on the relative error of a known target isotope (1/R 2T) and the other on the overall detection limit corrected by the relative error (1/DkR 2T). An automated Adaptive Variance-reduction Adjustment (AVA) tool is developed to iteratively define parameters for some variance reduction techniques in a problem with a target isotope. Sample problems demonstrate that AVA improves both precision and accuracy of a target result in an efficient manner

  18. Methods for the stable isotopic analysis of chlorine in chlorate and perchlorate compounds.

    PubMed

    Ader, M; Coleman, M L; Doyle, S P; Stroud, M; Wakelin, D

    2001-10-15

    Chlorate and perchlorate compounds, used as herbicides, solid fuel propellants, and explosives, are increasingly recognized as pollutants in groundwater. Stable isotope characterization would permit both environmental monitoring of extent of remediation and forensic characterization. Stoichiometric reduction to chloride (greater than 98% yield), by Fe(II) for chlorate and alkaline fusion-decomposition for perchlorate, allows analysis by standard methods to give highly reproducible and accurate delta37Cl results (0.05/1000, 2 x standard error). Analysis of various compounds from different suppliers yielded delta37Cl values for chlorate samples near to +0.2/1000 (SMOC), but one has within-sample heterogeneity of 0.5/1000, possibly due to crystallization processes during manufacture. Results for perchlorate samples also are generally near +0.2/1000, but one is +2.3/1000 (SMOC). The initial results suggest that both forensic and environmental applications might be feasible.

  19. Methods for the stable isotopic analysis of chlorine in chlorate and perchlorate compounds.

    PubMed

    Ader, M; Coleman, M L; Doyle, S P; Stroud, M; Wakelin, D

    2001-10-15

    Chlorate and perchlorate compounds, used as herbicides, solid fuel propellants, and explosives, are increasingly recognized as pollutants in groundwater. Stable isotope characterization would permit both environmental monitoring of extent of remediation and forensic characterization. Stoichiometric reduction to chloride (greater than 98% yield), by Fe(II) for chlorate and alkaline fusion-decomposition for perchlorate, allows analysis by standard methods to give highly reproducible and accurate delta37Cl results (0.05/1000, 2 x standard error). Analysis of various compounds from different suppliers yielded delta37Cl values for chlorate samples near to +0.2/1000 (SMOC), but one has within-sample heterogeneity of 0.5/1000, possibly due to crystallization processes during manufacture. Results for perchlorate samples also are generally near +0.2/1000, but one is +2.3/1000 (SMOC). The initial results suggest that both forensic and environmental applications might be feasible. PMID:11681470

  20. Isotopic analysis of dissolved organic carbon in produced water brines by wet chemical oxidation and cavity ring-down spectroscopy

    NASA Astrophysics Data System (ADS)

    Thomas, Randal; Conaway, Christopher; Saad, Nabil; Kharaka, Yousif

    2013-04-01

    Identification of fluid migration and escape from intentionally altered subsurface geologic systems, such as in hydraulic fracturing, enhanced oil recovery, and carbon sequestration activities, is an important issue for environmental regulators based on the traction that the "fracking" process is gathering across the United States. Given diverse injected fluid compositions and the potential for toxic or regulated compounds to be released, one of the most important steps in the process is accurately identifying evidence of injected fluid escape during and after injection processes. An important tool in identifying differences between the natural groundwater and injected fluid is the isotopic composition of dissolved constituents including inorganic components such as Sr and carbon isotopes of the dissolved organic compounds. Since biological processes in the mesothermal subsurface can rapidly alter the organic composition of a fluid, stable carbon isotopes of the dissolved organic compounds (DOC) are an effective means to identify differences in the origin of two fluids, especially when coupled with inorganic compound analyses. The burgeoning field of cavity ring-down spectroscopy (CRDS) for isotopic analysis presents an opportunity to obtain rapid, reliable and cost-effective isotopic measurements of DOC in potentially affected groundwater for the identification of leakage or the improvement of hydrogeochemical pathway models. Here we adapt the use of the novel hyphenated TOC-CRDS carbon isotope analyzer for the analysis of DOC in produced water by wet oxidation and describe the methods to evaluate performance and obtain useful information at higher salinities. Our methods are applied to a specific field example in a CO2-enhanced EOR field in Cranfield, Mississippi (USA) as a means to demonstrate the ability to distinguish natural and injected DOC using the stable isotopic composition of the dissolved organic carbon when employing the novel TOC-CRDS instrumentation

  1. Isotope ratio analysis of lead in blood and environmental samples by multi-collector inductively coupled plasma mass spectrometry.

    PubMed

    Takagi, Mai; Yoshinaga, Jun; Tanaka, Atsushi; Seyama, Haruhiko

    2011-01-01

    It is widely recognized that lead (Pb) affects children's cognitive function, even at relatively low blood lead levels (<10 µg dL(-1)). The determination of the source of Pb in children is essential for effective risk management. The use of multi-collector ICPMS (MC-ICPMS) for isotope ratio measurements of Pb in environmental and biological samples was examined for this purpose. MC-ICPMS with an instrumental mass fractionation correction by Tl allowed accurate isotope ratio measurements of the Pb isotopic reference material NIST SRM 981. However, the presence of matrix elements (Al, Ca, Fe and Na) at more than 10 mg kg(-1) in the sample solution significantly deteriorated the accuracy. The separation of Pb from the matrix is necessary for accurate measurements of the isotope ratio of Pb in environmental and biological samples. Bromide-complexation, followed by anion exchange was found to be satisfactory in terms of the recovery of Pb (90 to 104%) and the efficiency of matrix separation. The procedure was applied to a preliminary source analysis of Pb in the blood of Japanese children, and a significant contribution of indoor dust was demonstrated.

  2. Accurate fast method with high chemical yield for determination of uranium isotopes (234U, 235U, 238U) in granitic samples using alpha spectroscopy

    NASA Astrophysics Data System (ADS)

    Guirguis, Laila A.; Farag, Nagdy M.; Salim, Adham K.

    2015-03-01

    The present study aims to use the α-spectroscopy at Nuclear Materials Authority (NMA) of Egypt. A radiochemical technique for analysis uranium isotopes was carried out for ten mineralized granitic samples together with the International standards RGU-1 (IAEA) and St4 (NMA). Several steps of sample preparation, radiochemical separation and source preparation were performed before analysis. Uranium was separated from sample matrix with 0.2 M TOPO in cyclohexane as an extracting agent with a chemical yield 98.95% then uranium was purified from lanthanides and actinides present with 0.2 M TOA in xylene as an extracting agent. The pure fraction was electrodeposited on a mirror-polished copper disc from buffer solution (NaHSO4+H2SO4+NH4OH). Rectangle pt-electrode with an anode-cathode distance of 2 cm was used. Current was 900 mA and the electrodeposition time reach up to 120 min. The achieved results show that the chemical yield ranged between 87.9±6.8 and 98±8.6.

  3. Accurate and precise measurement of selenium by instrumental neutron activation analysis.

    PubMed

    Kim, In Jung; Watson, Russell P; Lindstrom, Richard M

    2011-05-01

    An accurate and precise measurement of selenium in Standard Reference Material (SRM) 3149, a primary calibration standard for the quantitative determination of selenium, has been accomplished by instrumental neutron activation analysis (INAA) in order to resolve a question arising during the certification process of the standard. Each limiting factor of the uncertainty in the activation analysis, including the sample preparation, irradiation, and γ-ray spectrometry steps, has been carefully monitored to minimize the uncertainty in the determined mass fraction. Neutron and γ-ray self-shielding within the elemental selenium INAA standards contributed most significantly to the uncertainty of the measurement. An empirical model compensating for neutron self-shielding and reducing the self-shielding uncertainty was successfully applied to these selenium standards. The mass fraction of selenium in the new lot of SRM 3149 was determined with a relative standard uncertainty of 0.6%.

  4. Subterranean Sympatry: An Investigation into Diet Using Stable Isotope Analysis

    PubMed Central

    Robb, Gillian N.; Woodborne, Stephan; Bennett, Nigel C.

    2012-01-01

    In the Western Cape three species of mole-rat occur in sympatry, however, little is known about differences in their dietary preferences. Dietary composition of the three species; the common mole-rat (Cryptomys hottentotus hottentotus), the Cape mole-rat (Georychus capensis) and the Cape dune mole-rat (Bathyergus suillus) were examined using stable isotope analysis. Blood, fur and claw samples were collected from 70 mole-rats, in addition to several potential food items, to assess food selection of the three species under natural conditions. Overall there was a significant difference in the isotopic composition (δ13C and δ15N) between all three species and significant differences in their diet composition. There were also significant differences between tissues in all three species suggesting temporal variation in diet. The small size and colonial lifestyle of C. h. hottentotus allows it to feed almost 100% on bulbs, while the solitary and larger species G. capensis and B. suillus fed to a greater extent on other resources such as grasses and clover. B. suillus, the largest of the species, had the most generalized diet. However, overall all species relied most heavily upon geophytes and consumed the same species suggesting competition for resources could exist. We also showed a high level of individual variation in diet choices. This was most pronounced in B. suillus and G. capensis and less so in C. h. hottentotus. We demonstrate that stable isotope analysis can successfully be applied to examine dietary patterns in subterranean mammals and provide insights into foraging patterns and dietary variation at both the inter and intra population level. PMID:23139795

  5. Accurate palm vein recognition based on wavelet scattering and spectral regression kernel discriminant analysis

    NASA Astrophysics Data System (ADS)

    Elnasir, Selma; Shamsuddin, Siti Mariyam; Farokhi, Sajad

    2015-01-01

    Palm vein recognition (PVR) is a promising new biometric that has been applied successfully as a method of access control by many organizations, which has even further potential in the field of forensics. The palm vein pattern has highly discriminative features that are difficult to forge because of its subcutaneous position in the palm. Despite considerable progress and a few practical issues, providing accurate palm vein readings has remained an unsolved issue in biometrics. We propose a robust and more accurate PVR method based on the combination of wavelet scattering (WS) with spectral regression kernel discriminant analysis (SRKDA). As the dimension of WS generated features is quite large, SRKDA is required to reduce the extracted features to enhance the discrimination. The results based on two public databases-PolyU Hyper Spectral Palmprint public database and PolyU Multi Spectral Palmprint-show the high performance of the proposed scheme in comparison with state-of-the-art methods. The proposed approach scored a 99.44% identification rate and a 99.90% verification rate [equal error rate (EER)=0.1%] for the hyperspectral database and a 99.97% identification rate and a 99.98% verification rate (EER=0.019%) for the multispectral database.

  6. Fast and accurate sensitivity analysis of IMPT treatment plans using Polynomial Chaos Expansion

    NASA Astrophysics Data System (ADS)

    Perkó, Zoltán; van der Voort, Sebastian R.; van de Water, Steven; Hartman, Charlotte M. H.; Hoogeman, Mischa; Lathouwers, Danny

    2016-06-01

    The highly conformal planned dose distribution achievable in intensity modulated proton therapy (IMPT) can severely be compromised by uncertainties in patient setup and proton range. While several robust optimization approaches have been presented to address this issue, appropriate methods to accurately estimate the robustness of treatment plans are still lacking. To fill this gap we present Polynomial Chaos Expansion (PCE) techniques which are easily applicable and create a meta-model of the dose engine by approximating the dose in every voxel with multidimensional polynomials. This Polynomial Chaos (PC) model can be built in an automated fashion relatively cheaply and subsequently it can be used to perform comprehensive robustness analysis. We adapted PC to provide among others the expected dose, the dose variance, accurate probability distribution of dose-volume histogram (DVH) metrics (e.g. minimum tumor or maximum organ dose), exact bandwidths of DVHs, and to separate the effects of random and systematic errors. We present the outcome of our verification experiments based on 6 head-and-neck (HN) patients, and exemplify the usefulness of PCE by comparing a robust and a non-robust treatment plan for a selected HN case. The results suggest that PCE is highly valuable for both research and clinical applications.

  7. Flow injection analysis-isotope ratio mass spectrometry for bulk carbon stable isotope analysis of alcoholic beverages.

    PubMed

    Jochmann, Maik A; Steinmann, Dirk; Stephan, Manuel; Schmidt, Torsten C

    2009-11-25

    A new method for bulk carbon isotope ratio determination of water-soluble samples is presented that is based on flow injection analysis-isotope ratio mass spectrometry (FIA-IRMS) using an LC IsoLink interface. Advantages of the method are that (i) only very small amounts of sample are required (2-5 microL of the sample for up to 200 possible injections), (ii) it avoids complex sample preparation procedures such as needed for EA-IRMS analysis (only sample dilution and injection,) and (iii) high throughput due to short analysis times is possible (approximately 15 min for five replicates). The method was first tested and evaluated as a fast screening method with industrially produced ethanol samples, and additionally the applicability was tested by the measurement of 81 alcoholic beverages, for example, whiskey, brandy, vodka, tequila, and others. The minimal sample concentration required for precise and reproducible measurements was around 50 microL L(-1) ethanol/water (1.71 mM carbon). The limit of repeatability was determined to be r=0.49%. FIA-IRMS represents a fast screening method for beverage authenticity control. Due to this, samples can be prescreened as a decisive criterion for more detailed investigations by HPLC-IRMS or multielement GC-IRMS measurements for a verification of adulteration. PMID:19856915

  8. An isotopic-independent highly accurate potential energy surface for CO2 isotopologues and an initial (12)C(16)O2 infrared line list.

    PubMed

    Huang, Xinchuan; Schwenke, David W; Tashkun, Sergey A; Lee, Timothy J

    2012-03-28

    An isotopic-independent, highly accurate potential energy surface (PES) has been determined for CO(2) by refining a purely ab initio PES with selected, purely experimentally determined rovibrational energy levels. The purely ab initio PES is denoted Ames-0, while the refined PES is denoted Ames-1. Detailed tests are performed to demonstrate the spectroscopic accuracy of the Ames-1 PES. It is shown that Ames-1 yields σ(rms) (root-mean-squares error) = 0.0156 cm(-1) for 6873 J = 0-117 (12)C(16)O(2) experimental energy levels, even though less than 500 (12)C(16)O(2) energy levels were included in the refinement procedure. It is also demonstrated that, without any additional refinement, Ames-1 yields very good agreement for isotopologues. Specifically, for the (12)C(16)O(2) and (13)C(16)O(2) isotopologues, spectroscopic constants G(v) computed from Ames-1 are within ±0.01 and 0.02 cm(-1) of reliable experimentally derived values, while for the (16)O(12)C(18)O, (16)O(12)C(17)O, (16)O(13)C(18)O, (16)O(13)C(17)O, (12)C(18)O(2), (17)O(12)C(18)O, (12)C(17)O(2), (13)C(18)O(2), (13)C(17)O(2), (17)O(13)C(18)O, and (14)C(16)O(2) isotopologues, the differences are between ±0.10 and 0.15 cm(-1). To our knowledge, this is the first time a polyatomic PES has been refined using such high J values, and this has led to new challenges in the refinement procedure. An initial high quality, purely ab initio dipole moment surface (DMS) is constructed and used to generate a 296 K line list. For most bands, experimental IR intensities are well reproduced for (12)C(16)O(2) using Ames-1 and the DMS. For more than 80% of the bands, the experimental intensities are reproduced with σ(rms)(ΔI) < 20% or σ(rms)(ΔI∕δ(obs)) < 5. A few exceptions are analyzed and discussed. Directions for future improvements are discussed, though it is concluded that the current Ames-1 and the DMS should be useful in analyzing and assigning high-resolution laboratory or astronomical spectra. PMID:22462861

  9. Quantitative analysis of volatiles in edible oils following accelerated oxidation using broad spectrum isotope standards

    PubMed Central

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

    2014-01-01

    Analysis of food volatiles generated by processing are widely reported but comparisons across studies is challenging in part because most reports are inherently semi-quantitative for most analytes due to limited availability of chemical standards. We recently introduced a novel strategy for creation of broad spectrum isotopic standards for accurate quantitative food chemical analysis. Here we apply the principle to quantification of 25 volatiles in seven thermally oxidized edible oils. After extended oxidation, total volatiles of high n-3 oils (flax, fish, cod liver) were 120-170 mg/kg while low n-3 vegetable oils were <50 mg/kg. Separate experiments on thermal degradation of d5-ethyl linolenate indicate that off-aroma volatiles originate throughout the n-3 molecule and not solely the n-3 terminal end. These data represent the first report using broad-spectrum isotopically labeled standards for quantitative characterization of processing-induced volatile generation across related foodstuffs, and verify the origin of specific volatiles from parent n-3 fatty acids. PMID:25529686

  10. Evaluation of 13C isotopic tracers for metabolic flux analysis in mammalian cells

    PubMed Central

    Metallo, Christian M.; Walther, Jason L.; Stephanopoulos, Gregory

    2009-01-01

    13C metabolic flux analysis (MFA) is the most comprehensive means of characterizing cellular metabolic states. Uniquely labeled isotopic tracers enable more focused analyses to probe specific reactions within the network. As a result, the choice of tracer largely determines the precision with which one can estimate metabolic fluxes, especially in complex mammalian systems that require multiple substrates. Here we have experimentally determined metabolic fluxes in a tumor cell line, successfully recapitulating the hallmarks of cancer cell metabolism. Using these data, we computationally evaluated specifically labeled 13C glucose and glutamine tracers for their ability to precisely and accurately estimate fluxes in central carbon metabolism. These methods enabled us to to identify the optimal tracer for analyzing individual fluxes, specific pathways, and central carbon metabolism as a whole. [1,2-13C2]glucose provided the most precise estimates for glycolysis, the pentose phosphate pathway, and the overall network. Tracers such as [2-13C]glucose and [3-13C]glucose also outperformed the more commonly used [1-13C]glucose. [U-13C5]glutamine emerged as the preferred isotopic tracer for analysis of the tricarboxylic acid (TCA) cycle. These results provide valuable, quantitative information on the performance of 13C-labeled substrates and can aid in the design of more informative MFA experiments in mammalian cell culture. PMID:19622376

  11. 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.

  12. Forensic isotope analysis to refine a hydrologic conceptual model.

    PubMed

    Bassett, R L; Steinwand, Aaron; Jorat, Saeed; Petersen, Christian; Jackson, Randy

    2008-01-01

    Water resources in the arid southwestern United States are frequently the subject of conflict from competing private and public interests. Legal remedies may remove impasses, but the technical analysis of the problem often determines the future success of legal solutions. In Owens Valley, California, the source of water for the Los Angeles Aqueduct (LAA) is flow diverted from the Owens River and its tributaries and ground water from valley aquifers. Future management of ground water delivered to the LAA needs technical support regarding quantity available, interconnection of shallow and confined aquifers, impact on local springs, and rate of recharge. Ground water flow models and ground water composition are tools already in use, but these have large uncertainty for local interpretations. This study conducted targeted sampling of springs and wells to evaluate the hydrologic system to corroborate conceptual and numerical models. The effort included measurement of intrinsic isotopic composition at key locations in the aquifers. The stable isotopic data of boron (delta(11)B), sulfur (delta(34)S), oxygen (delta(18)O), hydrogen (delta D), and tritium ((3)H) supported by basic chemical data provided rules for characterizing the upper and the lower aquifer system, confirmed the interpretation of ground water flow near faults and flow barriers, and detected hydraulic connections between the LAA and the perennial springs at key locations along the unlined reach of the LAA. This study exemplifies the use of forensic isotopic approaches as independent checks on the consistency of interpretations of conceptual models of a ground water system and the numerical hydrologic simulations.

  13. Time-Accurate Simulations and Acoustic Analysis of Slat Free-Shear Layer

    NASA Technical Reports Server (NTRS)

    Khorrami, Mehdi R.; Singer, Bart A.; Berkman, Mert E.

    2001-01-01

    A detailed computational aeroacoustic analysis of a high-lift flow field is performed. Time-accurate Reynolds Averaged Navier-Stokes (RANS) computations simulate the free shear layer that originates from the slat cusp. Both unforced and forced cases are studied. Preliminary results show that the shear layer is a good amplifier of disturbances in the low to mid-frequency range. The Ffowcs-Williams and Hawkings equation is solved to determine the acoustic field using the unsteady flow data from the RANS calculations. The noise radiated from the excited shear layer has a spectral shape qualitatively similar to that obtained from measurements in a corresponding experimental study of the high-lift system.

  14. Global analysis of the Deinococcus radiodurans proteome by using accurate mass tags

    PubMed Central

    Lipton, Mary S.; Paša-Tolić, Ljiljana; Anderson, Gordon A.; Anderson, David J.; Auberry, Deanna L.; Battista, John R.; Daly, Michael J.; Fredrickson, Jim; Hixson, Kim K.; Kostandarithes, Heather; Masselon, Christophe; Markillie, Lye Meng; Moore, Ronald J.; Romine, Margaret F.; Shen, Yufeng; Stritmatter, Eric; Tolić, Nikola; Udseth, Harold R.; Venkateswaran, Amudhan; Wong, Kwong-Kwok; Zhao, Rui; Smith, Richard D.

    2002-01-01

    Understanding biological systems and the roles of their constituents is facilitated by the ability to make quantitative, sensitive, and comprehensive measurements of how their proteome changes, e.g., in response to environmental perturbations. To this end, we have developed a high-throughput methodology to characterize an organism's dynamic proteome based on the combination of global enzymatic digestion, high-resolution liquid chromatographic separations, and analysis by Fourier transform ion cyclotron resonance mass spectrometry. The peptides produced serve as accurate mass tags for the proteins and have been used to identify with high confidence >61% of the predicted proteome for the ionizing radiation-resistant bacterium Deinococcus radiodurans. This fraction represents the broadest proteome coverage for any organism to date and includes 715 proteins previously annotated as either hypothetical or conserved hypothetical. PMID:12177431

  15. Toward Sensitive and Accurate Analysis of Antibody Biotherapeutics by Liquid Chromatography Coupled with Mass Spectrometry

    PubMed Central

    An, Bo; Zhang, Ming

    2014-01-01

    Remarkable methodological advances in the past decade have expanded the application of liquid chromatography coupled with mass spectrometry (LC/MS) analysis of biotherapeutics. Currently, LC/MS represents a promising alternative or supplement to the traditional ligand binding assay (LBA) in the pharmacokinetic, pharmacodynamic, and toxicokinetic studies of protein drugs, owing to the rapid and cost-effective method development, high specificity and reproducibility, low sample consumption, the capacity of analyzing multiple targets in one analysis, and the fact that a validated method can be readily adapted across various matrices and species. While promising, technical challenges associated with sensitivity, sample preparation, method development, and quantitative accuracy need to be addressed to enable full utilization of LC/MS. This article introduces the rationale and technical challenges of LC/MS techniques in biotherapeutics analysis and summarizes recently developed strategies to alleviate these challenges. Applications of LC/MS techniques on quantification and characterization of antibody biotherapeutics are also discussed. We speculate that despite the highly attractive features of LC/MS, it will not fully replace traditional assays such as LBA in the foreseeable future; instead, the forthcoming trend is likely the conjunction of biochemical techniques with versatile LC/MS approaches to achieve accurate, sensitive, and unbiased characterization of biotherapeutics in highly complex pharmaceutical/biologic matrices. Such combinations will constitute powerful tools to tackle the challenges posed by the rapidly growing needs for biotherapeutics development. PMID:25185260

  16. Quantitation and accurate mass analysis of pesticides in vegetables by LC/TOF-MS.

    PubMed

    Ferrer, Imma; Thurman, E Michael; Fernández-Alba, Amadeo R

    2005-05-01

    A quantitative method consisting of solvent extraction followed by liquid chromatography/time-of-flight mass spectrometry (LC/TOF-MS) analysis was developed for the identification and quantitation of three chloronicotinyl pesticides (imidacloprid, acetamiprid, thiacloprid) commonly used on salad vegetables. Accurate mass measurements within 3 ppm error were obtained for all the pesticides studied in various vegetable matrixes (cucumber, tomato, lettuce, pepper), which allowed an unequivocal identification of the target pesticides. Calibration curves covering 2 orders of magnitude were linear over the concentration range studied, thus showing the quantitative ability of TOF-MS as a monitoring tool for pesticides in vegetables. Matrix effects were also evaluated using matrix-matched standards showing no significant interferences between matrixes and clean extracts. Intraday reproducibility was 2-3% relative standard deviation (RSD) and interday values were 5% RSD. The precision (standard deviation) of the mass measurements was evaluated and it was less than 0.23 mDa between days. Detection limits of the chloronicotinyl insecticides in salad vegetables ranged from 0.002 to 0.01 mg/kg. These concentrations are equal to or better than the EU directives for controlled pesticides in vegetables showing that LC/TOF-MS analysis is a powerful tool for identification of pesticides in vegetables. Robustness and applicability of the method was validated for the analysis of market vegetable samples. Concentrations found in these samples were in the range of 0.02-0.17 mg/kg of vegetable. PMID:15859598

  17. Spectral analysis software improves confidence in plant and soil water stable isotope analyses performed by isotope ratio infrared spectroscopy (IRIS).

    PubMed

    West, A G; Goldsmith, G R; Matimati, I; Dawson, T E

    2011-08-30

    Previous studies have demonstrated the potential for large errors to occur when analyzing waters containing organic contaminants using isotope ratio infrared spectroscopy (IRIS). In an attempt to address this problem, IRIS manufacturers now provide post-processing spectral analysis software capable of identifying samples with the types of spectral interference that compromises their stable isotope analysis. Here we report two independent tests of this post-processing spectral analysis software on two IRIS systems, OA-ICOS (Los Gatos Research Inc.) and WS-CRDS (Picarro Inc.). Following a similar methodology to a previous study, we cryogenically extracted plant leaf water and soil water and measured the δ(2)H and δ(18)O values of identical samples by isotope ratio mass spectrometry (IRMS) and IRIS. As an additional test, we analyzed plant stem waters and tap waters by IRMS and IRIS in an independent laboratory. For all tests we assumed that the IRMS value represented the "true" value against which we could compare the stable isotope results from the IRIS methods. Samples showing significant deviations from the IRMS value (>2σ) were considered to be contaminated and representative of spectral interference in the IRIS measurement. Over the two studies, 83% of plant species were considered contaminated on OA-ICOS and 58% on WS-CRDS. Post-analysis, spectra were analyzed using the manufacturer's spectral analysis software, in order to see if the software correctly identified contaminated samples. In our tests the software performed well, identifying all the samples with major errors. However, some false negatives indicate that user evaluation and testing of the software are necessary. Repeat sampling of plants showed considerable variation in the discrepancies between IRIS and IRMS. As such, we recommend that spectral analysis of IRIS data must be incorporated into standard post-processing routines. Furthermore, we suggest that the results from spectral analysis be

  18. Capillary absorption spectrometer and process for isotopic analysis of small samples

    DOEpatents

    Alexander, M. Lizabeth; Kelly, James F.; Sams, Robert L.; Moran, James J.; Newburn, Matthew K.; Blake, Thomas A.

    2016-03-29

    A capillary absorption spectrometer and process are described that provide highly sensitive and accurate stable absorption measurements of analytes in a sample gas that may include isotopologues of carbon and oxygen obtained from gas and biological samples. It further provides isotopic images of microbial communities that allow tracking of nutrients at the single cell level. It further targets naturally occurring variations in carbon and oxygen isotopes that avoids need for expensive isotopically labeled mixtures which allows study of samples taken from the field without modification. The method also permits sampling in vivo permitting real-time ambient studies of microbial communities.

  19. Oxygen isotope corrections for online δ34S analysis

    USGS Publications Warehouse

    Fry, B.; Silva, S.R.; Kendall, C.; Anderson, R.K.

    2002-01-01

    Elemental analyzers have been successfully coupled to stable-isotope-ratio mass spectrometers for online measurements of the δ34S isotopic composition of plants, animals and soils. We found that the online technology for automated δ34S isotopic determinations did not yield reproducible oxygen isotopic compositions in the SO2 produced, and as a result calculated δ34S values were often 1–3‰ too high versus their correct values, particularly for plant and animal samples with high C/S ratio. Here we provide empirical and analytical methods for correcting the S isotope values for oxygen isotope variations, and further detail a new SO2-SiO2 buffering method that minimizes detrimental oxygen isotope variations in SO2.

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

    PubMed

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

    2015-07-01

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

  1. Analysis of the site-specific carbon isotope composition of propane by gas source isotope ratio mass spectrometer

    NASA Astrophysics Data System (ADS)

    Piasecki, Alison; Sessions, Alex; Lawson, Michael; Ferreira, A. A.; Neto, E. V. Santos; Eiler, John M.

    2016-09-01

    Site-specific isotope ratio measurements potentially provide valuable information about the formation and degradation of complex molecules-information that is lost in conventional bulk isotopic measurements. Here we discuss the background and possible applications of such measurements, and present a technique for studying the site-specific carbon isotope composition of propane at natural abundance based on mass spectrometric analysis of the intact propane molecule and its fragment ions. We demonstrate the feasibility of this approach through measurements of mixtures of natural propane and propane synthesized with site-specific 13C enrichment, and we document the limits of precision of our technique. We show that mass balance calculations of the bulk δ13C of propane based on our site-specific measurements is generally consistent with independent constraints on bulk δ13C. We further demonstrate the accuracy of the technique, and illustrate one of its simpler applications by documenting the site-specific carbon isotope signature associated with gas phase diffusion of propane, confirming that our measurements conform to the predictions of the kinetic theory of gases. This method can be applied to propane samples of moderate size (tens of micromoles) isolated from natural gases. Thus, it provides a means of studying the site-specific stable isotope systematics of propane at natural isotope abundances on sample sizes that are readily recovered from many natural environments. This method may also serve as a model for future techniques that apply high-resolution mass spectrometry to study the site-specific isotopic distributions of larger organic molecules, with potential applications to biosynthesis, forensics and other geochemical subjects.

  2. Noise-free accurate count of microbial colonies by time-lapse shadow image analysis.

    PubMed

    Ogawa, Hiroyuki; Nasu, Senshi; Takeshige, Motomu; Funabashi, Hisakage; Saito, Mikako; Matsuoka, Hideaki

    2012-12-01

    Microbial colonies in food matrices could be counted accurately by a novel noise-free method based on time-lapse shadow image analysis. An agar plate containing many clusters of microbial colonies and/or meat fragments was trans-illuminated to project their 2-dimensional (2D) shadow images on a color CCD camera. The 2D shadow images of every cluster distributed within a 3-mm thick agar layer were captured in focus simultaneously by means of a multiple focusing system, and were then converted to 3-dimensional (3D) shadow images. By time-lapse analysis of the 3D shadow images, it was determined whether each cluster comprised single or multiple colonies or a meat fragment. The analytical precision was high enough to be able to distinguish a microbial colony from a meat fragment, to recognize an oval image as two colonies contacting each other, and to detect microbial colonies hidden under a food fragment. The detection of hidden colonies is its outstanding performance in comparison with other systems. The present system attained accuracy for counting fewer than 5 colonies and is therefore of practical importance.

  3. Enantiomeric separation in comprehensive two-dimensional gas chromatography with accurate mass analysis.

    PubMed

    Chin, Sung-Tong; Nolvachai, Yada; Marriott, Philip J

    2014-11-01

    Chiral comprehensive two-dimensional gas chromatography (eGC×GC) coupled to quadrupole-accurate mass time-of-flight mass spectrometry (QTOFMS) was evaluated for its capability to report the chiral composition of several monoterpenes, namely, α-pinene, β-pinene, and limonene in cardamom oil. Enantiomers in a standard mixture were fully resolved by direct enantiomeric-GC analysis with a 2,3-di-O-methyl-6-t-butylsilyl derivatized β-cyclodextrin phase; however, the (+)-(R)-limonene enantiomer in cardamom oil was overlapped with other background components including cymene and cineole. Verification of (+)-(R)-limonene components based on characteristic ions at m/z 136, 121, and 107 acquired by chiral single-dimension GC-QTOFMS in the alternate MS/MSMS mode of operation was unsuccessful due to similar parent/daughter ions generated by interfering or co-eluting cymene and cineole. Column phases SUPELCOWAX, SLB-IL111, HP-88, and SLB-IL59, were incorporated as the second dimension column ((2)D) in chiral GC×GC analysis; the SLB-IL59 offered the best resolution for the tested monoterpene enantiomers from the matrix background. Enantiomeric ratios for α-pinene, β-pinene, and limonene were determined to be 1.325, 2.703, and 1.040, respectively, in the cardamom oil sample based on relative peak area data. PMID:24420979

  4. An accurate skull stripping method based on simplex meshes and histogram analysis for magnetic resonance images.

    PubMed

    Galdames, Francisco J; Jaillet, Fabrice; Perez, Claudio A

    2012-01-01

    Skull stripping methods are designed to eliminate the non-brain tissue in magnetic resonance (MR) brain images. Removal of non-brain tissues is a fundamental step in enabling the processing of brain MR images. The aim of this study is to develop an automatic accurate skull stripping method based on deformable models and histogram analysis. A rough-segmentation step is used to find the optimal starting point for the deformation and is based on thresholds and morphological operators. Thresholds are computed using comparisons with an atlas, and modeling by Gaussians. The deformable model is based on a simplex mesh and its deformation is controlled by the image local gray levels and the information obtained on the gray level modeling of the rough-segmentation. Our Simplex Mesh and Histogram Analysis Skull Stripping (SMHASS) method was tested on the following international databases commonly used in scientific articles: BrainWeb, Internet Brain Segmentation Repository (IBSR), and Segmentation Validation Engine (SVE). A comparison was performed against three of the best skull stripping methods previously published: Brain Extraction Tool (BET), Brain Surface Extractor (BSE), and Hybrid Watershed Algorithm (HWA). Performance was measured using the Jaccard index (J) and Dice coefficient (κ). Our method showed the best performance and differences were statistically significant (p<0.05): J=0.904 and κ=0.950 on BrainWeb; J=0.905 and κ=0.950 on IBSR; J=0.946 and κ=0.972 on SVE.

  5. Accurate airway segmentation based on intensity structure analysis and graph-cut

    NASA Astrophysics Data System (ADS)

    Meng, Qier; Kitsaka, Takayuki; Nimura, Yukitaka; Oda, Masahiro; Mori, Kensaku

    2016-03-01

    This paper presents a novel airway segmentation method based on intensity structure analysis and graph-cut. Airway segmentation is an important step in analyzing chest CT volumes for computerized lung cancer detection, emphysema diagnosis, asthma diagnosis, and pre- and intra-operative bronchoscope navigation. However, obtaining a complete 3-D airway tree structure from a CT volume is quite challenging. Several researchers have proposed automated algorithms basically based on region growing and machine learning techniques. However these methods failed to detect the peripheral bronchi branches. They caused a large amount of leakage. This paper presents a novel approach that permits more accurate extraction of complex bronchial airway region. Our method are composed of three steps. First, the Hessian analysis is utilized for enhancing the line-like structure in CT volumes, then a multiscale cavity-enhancement filter is employed to detect the cavity-like structure from the previous enhanced result. In the second step, we utilize the support vector machine (SVM) to construct a classifier for removing the FP regions generated. Finally, the graph-cut algorithm is utilized to connect all of the candidate voxels to form an integrated airway tree. We applied this method to sixteen cases of 3D chest CT volumes. The results showed that the branch detection rate of this method can reach about 77.7% without leaking into the lung parenchyma areas.

  6. Enantiomeric separation in comprehensive two-dimensional gas chromatography with accurate mass analysis.

    PubMed

    Chin, Sung-Tong; Nolvachai, Yada; Marriott, Philip J

    2014-11-01

    Chiral comprehensive two-dimensional gas chromatography (eGC×GC) coupled to quadrupole-accurate mass time-of-flight mass spectrometry (QTOFMS) was evaluated for its capability to report the chiral composition of several monoterpenes, namely, α-pinene, β-pinene, and limonene in cardamom oil. Enantiomers in a standard mixture were fully resolved by direct enantiomeric-GC analysis with a 2,3-di-O-methyl-6-t-butylsilyl derivatized β-cyclodextrin phase; however, the (+)-(R)-limonene enantiomer in cardamom oil was overlapped with other background components including cymene and cineole. Verification of (+)-(R)-limonene components based on characteristic ions at m/z 136, 121, and 107 acquired by chiral single-dimension GC-QTOFMS in the alternate MS/MSMS mode of operation was unsuccessful due to similar parent/daughter ions generated by interfering or co-eluting cymene and cineole. Column phases SUPELCOWAX, SLB-IL111, HP-88, and SLB-IL59, were incorporated as the second dimension column ((2)D) in chiral GC×GC analysis; the SLB-IL59 offered the best resolution for the tested monoterpene enantiomers from the matrix background. Enantiomeric ratios for α-pinene, β-pinene, and limonene were determined to be 1.325, 2.703, and 1.040, respectively, in the cardamom oil sample based on relative peak area data.

  7. Isotopic gas analysis through Purcell cavity enhanced Raman scattering

    NASA Astrophysics Data System (ADS)

    Petrak, B.; Cooper, J.; Konthasinghe, K.; Peiris, M.; Djeu, N.; Hopkins, A. J.; Muller, A.

    2016-02-01

    Purcell enhanced Raman scattering (PERS) by means of a doubly resonant Fabry-Perot microcavity (mode volume ≈ 100 μm3 and finesse ≈ 30 000) has been investigated as a technique for isotopic ratio gas analysis. At the pump frequency, the resonant cavity supports a buildup of circulating power while simultaneously enabling Purcell spontaneous emission rate enhancement at the resonant Stokes frequency. The three most common isotopologues of CO2 gas were quantified, and a signal was obtained from 13C16O2 down to a partial pressure of 2 Torr. Due to its small size and low pump power needed (˜10 mW) PERS lends itself to miniaturization. Furthermore, since the cavity is resonant with the emission frequency, future improvements could allow it to serve as its own spectral analyzer and no separate spectroscopic device would be needed.

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

    PubMed

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

    2015-01-01

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

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

    PubMed

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

    2015-01-01

    We investigated a novel application of stable isotope abundance analysis of nitrogen (15N), carbon (13C), hydrogen (2H), and oxygen (18O) to characterize pen ink. We focused on both ballpoint and gel pen inks. We found that the isotope ratios of ink from pens purchased together in a package were similar and within-package stable isotope ratio variability was not significantly larger than the variability of isotope reference materials used during analysis. In contrast, the isotope ratios of ink from pens of the same brand purchased in three states of the continental USA were significantly different from each other and there was isotope ratio variation among pens of the same brand but different, unknown production periods. The stable isotope ratios of inked paper were statistically distinguishable using measured δ15N values. Paper inked with different gel pens was statistically distinguishable using measured δ2H values. The capacity of stable isotope ratios to differentiate among ballpoint inks as well as gel inks shows that stable isotope analysis may be a useful and quantifiable investigative technique for questioned document examination, although current sample size requirements limit its utility. Application of the technique in casework will require the development of micro-scale sampling and analysis methods. PMID:25577004

  10. Fully Automatic System for Accurate Localisation and Analysis of Cephalometric Landmarks in Lateral Cephalograms

    PubMed Central

    Lindner, Claudia; Wang, Ching-Wei; Huang, Cheng-Ta; Li, Chung-Hsing; Chang, Sheng-Wei; Cootes, Tim F.

    2016-01-01

    Cephalometric tracing is a standard analysis tool for orthodontic diagnosis and treatment planning. The aim of this study was to develop and validate a fully automatic landmark annotation (FALA) system for finding cephalometric landmarks in lateral cephalograms and its application to the classification of skeletal malformations. Digital cephalograms of 400 subjects (age range: 7–76 years) were available. All cephalograms had been manually traced by two experienced orthodontists with 19 cephalometric landmarks, and eight clinical parameters had been calculated for each subject. A FALA system to locate the 19 landmarks in lateral cephalograms was developed. The system was evaluated via comparison to the manual tracings, and the automatically located landmarks were used for classification of the clinical parameters. The system achieved an average point-to-point error of 1.2 mm, and 84.7% of landmarks were located within the clinically accepted precision range of 2.0 mm. The automatic landmark localisation performance was within the inter-observer variability between two clinical experts. The automatic classification achieved an average classification accuracy of 83.4% which was comparable to an experienced orthodontist. The FALA system rapidly and accurately locates and analyses cephalometric landmarks in lateral cephalograms, and has the potential to significantly improve the clinical work flow in orthodontic treatment. PMID:27645567

  11. Spectral neighbor analysis method for automated generation of quantum-accurate interatomic potentials

    SciTech Connect

    Thompson, A.P.; Swiler, L.P.; Trott, C.R.; Foiles, S.M.; Tucker, G.J.

    2015-03-15

    We present a new interatomic potential for solids and liquids called Spectral Neighbor Analysis Potential (SNAP). The SNAP potential has a very general form and uses machine-learning techniques to reproduce the energies, forces, and stress tensors of a large set of small configurations of atoms, which are obtained using high-accuracy quantum electronic structure (QM) calculations. The local environment of each atom is characterized by a set of bispectrum components of the local neighbor density projected onto a basis of hyperspherical harmonics in four dimensions. The bispectrum components are the same bond-orientational order parameters employed by the GAP potential [1]. The SNAP potential, unlike GAP, assumes a linear relationship between atom energy and bispectrum components. The linear SNAP coefficients are determined using weighted least-squares linear regression against the full QM training set. This allows the SNAP potential to be fit in a robust, automated manner to large QM data sets using many bispectrum components. The calculation of the bispectrum components and the SNAP potential are implemented in the LAMMPS parallel molecular dynamics code. We demonstrate that a previously unnoticed symmetry property can be exploited to reduce the computational cost of the force calculations by more than one order of magnitude. We present results for a SNAP potential for tantalum, showing that it accurately reproduces a range of commonly calculated properties of both the crystalline solid and the liquid phases. In addition, unlike simpler existing potentials, SNAP correctly predicts the energy barrier for screw dislocation migration in BCC tantalum.

  12. Fully Automatic System for Accurate Localisation and Analysis of Cephalometric Landmarks in Lateral Cephalograms.

    PubMed

    Lindner, Claudia; Wang, Ching-Wei; Huang, Cheng-Ta; Li, Chung-Hsing; Chang, Sheng-Wei; Cootes, Tim F

    2016-09-20

    Cephalometric tracing is a standard analysis tool for orthodontic diagnosis and treatment planning. The aim of this study was to develop and validate a fully automatic landmark annotation (FALA) system for finding cephalometric landmarks in lateral cephalograms and its application to the classification of skeletal malformations. Digital cephalograms of 400 subjects (age range: 7-76 years) were available. All cephalograms had been manually traced by two experienced orthodontists with 19 cephalometric landmarks, and eight clinical parameters had been calculated for each subject. A FALA system to locate the 19 landmarks in lateral cephalograms was developed. The system was evaluated via comparison to the manual tracings, and the automatically located landmarks were used for classification of the clinical parameters. The system achieved an average point-to-point error of 1.2 mm, and 84.7% of landmarks were located within the clinically accepted precision range of 2.0 mm. The automatic landmark localisation performance was within the inter-observer variability between two clinical experts. The automatic classification achieved an average classification accuracy of 83.4% which was comparable to an experienced orthodontist. The FALA system rapidly and accurately locates and analyses cephalometric landmarks in lateral cephalograms, and has the potential to significantly improve the clinical work flow in orthodontic treatment.

  13. Accurate mass tag retention time database for urine proteome analysis by chromatography--mass spectrometry.

    PubMed

    Agron, I A; Avtonomov, D M; Kononikhin, A S; Popov, I A; Moshkovskii, S A; Nikolaev, E N

    2010-05-01

    Information about peptides and proteins in urine can be used to search for biomarkers of early stages of various diseases. The main technology currently used for identification of peptides and proteins is tandem mass spectrometry, in which peptides are identified by mass spectra of their fragmentation products. However, the presence of the fragmentation stage decreases sensitivity of analysis and increases its duration. We have developed a method for identification of human urinary proteins and peptides. This method based on the accurate mass and time tag (AMT) method does not use tandem mass spectrometry. The database of AMT tags containing more than 1381 AMT tags of peptides has been constructed. The software for database filling with AMT tags, normalizing the chromatograms, database application for identification of proteins and peptides, and their quantitative estimation has been developed. The new procedures for peptide identification by tandem mass spectra and the AMT tag database are proposed. The paper also lists novel proteins that have been identified in human urine for the first time. PMID:20632944

  14. Fully Automatic System for Accurate Localisation and Analysis of Cephalometric Landmarks in Lateral Cephalograms.

    PubMed

    Lindner, Claudia; Wang, Ching-Wei; Huang, Cheng-Ta; Li, Chung-Hsing; Chang, Sheng-Wei; Cootes, Tim F

    2016-01-01

    Cephalometric tracing is a standard analysis tool for orthodontic diagnosis and treatment planning. The aim of this study was to develop and validate a fully automatic landmark annotation (FALA) system for finding cephalometric landmarks in lateral cephalograms and its application to the classification of skeletal malformations. Digital cephalograms of 400 subjects (age range: 7-76 years) were available. All cephalograms had been manually traced by two experienced orthodontists with 19 cephalometric landmarks, and eight clinical parameters had been calculated for each subject. A FALA system to locate the 19 landmarks in lateral cephalograms was developed. The system was evaluated via comparison to the manual tracings, and the automatically located landmarks were used for classification of the clinical parameters. The system achieved an average point-to-point error of 1.2 mm, and 84.7% of landmarks were located within the clinically accepted precision range of 2.0 mm. The automatic landmark localisation performance was within the inter-observer variability between two clinical experts. The automatic classification achieved an average classification accuracy of 83.4% which was comparable to an experienced orthodontist. The FALA system rapidly and accurately locates and analyses cephalometric landmarks in lateral cephalograms, and has the potential to significantly improve the clinical work flow in orthodontic treatment. PMID:27645567

  15. Multivariate Stable Isotope Analysis to Determine Linkages between Benzocaine Seizures

    NASA Astrophysics Data System (ADS)

    Kemp, H. F.; Meier-Augenstein, W.; Collins, M.; Salouros, H.; Cunningham, A.; Harrison, M.

    2012-04-01

    In July 2010, a woman was jailed for nine years in the UK after the prosecution successfully argued that attempting to import a cutting agent was proof of involvement in a conspiracy to supply Cocaine. That landmark ruling provided law enforcement agencies with much greater scope to tackle those involved in this aspect of the drug trade, specifically targeting those importing the likes of benzocaine or lidocaine. Huge quantities of these compounds are imported into the UK and between May and August 2010, four shipments of Benzocaine amounting to more then 4 tons had been seized as part of Operation Kitley, a joint initiative between the UK Border Agency and the Serious Organised Crime Agency (SOCA). By diluting cocaine, traffickers can make it go a lot further for very little cost, leading to huge profits. In recent years, dealers have moved away from inert substances, like sugar and baby milk powder, in favour of active pharmaceutical ingredients (APIs), including anaesthetics like Benzocaine and Lidocaine. Both these mimic the numbing effect of cocaine, and resemble it closely in colour, texture and some chemical behaviours, making it easier to conceal the fact that the drug has been diluted. API cutting agents have helped traffickers to maintain steady supplies in the face of successful interdiction and even expand the market in the UK, particularly to young people aged from their mid teens to early twenties. From importation to street-level, the purity of the drug can be reduced up to a factor of 80 and street level cocaine can have a cocaine content as low as 1%. In view of the increasing use of Benzocaine as cutting agent for Cocaine, a study was carried out to investigate if 2H, 13C, 15N and 18O stable isotope signatures could be used in conjunction with multivariate chemometric data analysis to determine potential linkage between benzocaine exhibits seized from different locations or individuals to assist with investigation and prosecution of drug

  16. Field calibration of stable isotopes (δ18O) in coccoliths : Toward an accurate carbonate record-based reconstruction of the photic zone temperature

    NASA Astrophysics Data System (ADS)

    Candelier, Y.; Minoletti, F.; Hermoso, M.; Probert, I.

    2010-12-01

    Oxygen-isotopes from biogenic carbonates have been widely used to estimate SSTs during the Cenozoic. The full potential of coccolithophores for reconstructing past temperatures is still unexploited owing to two major issues: their minute size that prevents their isotopic analyzes at the specific level as done for foraminifera, and the large range of interspecific isotopic offsets (~ 5‰) ascribed to the vital effect (Ziveri et al., 2003). To test the suitability of applying in vitro data for the truly pelagic natural record, we established new coccolithophorid δ18O-temperature calibrations from sediments that we compared to empirical thermodependance equations from previous culture experiments. In this respect, we focused on two foremost coccolithophore species: Calcidicus leptoporus and Gephyrocapsa oceanica. We successfully obtained monospecific fractions of those taxa by applying a microfiltering protocol (Minoletti et al., 2009) on Holocene sediments for which the temperature of the photic zone water has been directly measured. For G. oceanica, the constant offset (δcGo-δceq) of ~ +1.5‰ with respect to equilibrium is in a good agreement with previous culture experiments (~ +1.6‰; Ziveri et al., 2003). Conversely, for C. leptoporus, although the relation between temperature and oxygen-isotopic fractionation is also well-behaved between 16 and 27°C, we found a significant discrepancy with previous cultures (-2.8‰; Dudley et al., 1986). This difference could be the result of growing conditions in the lab that may not mimate the natural environment (seawater chemistry such as pH, nutrient level, cell concentration, …). We generated new isotopic results of preliminary temperature-controlled experiments for C. leptoporus in constrained conditions close to the natural environment. We measured an isotopic offset comparable to the one from our sedimentologic study. Hence, we suggest a new correction of -1.2‰ for C. leptoporus, which may be more

  17. Quantitative Analysis by Isotopic Dilution Using Mass Spectroscopy: The Determination of Caffeine by GC-MS.

    ERIC Educational Resources Information Center

    Hill, Devon W.; And Others

    1988-01-01

    Describes a laboratory technique for quantitative analysis of caffeine by an isotopic dilution method for coupled gas chromatography-mass spectroscopy. Discusses caffeine analysis and experimental methodology. Lists sample caffeine concentrations found in common products. (MVL)

  18. A new method for carbon isotopic analysis of protein

    SciTech Connect

    Nelson, D.E. )

    1991-02-01

    The reaction of ninhydrin with amino acids can be used in carbon isotopic studies of protein. The reaction can be applied to extract as carbon dioxide only peptide-bonded carbon in proteinaceous material, thus avoiding most, if not all, contaminants. Test radiocarbon dates on ancient bone indicate that the method provides reliable ages, and stable carbon isotopic data suggest that our understanding of isotopic dietary reconstruction needs detailed examination. The technique should also be useful in biochemical tracing experiments and in global carbon budget studies, and the underlying principle may be applicable to other isotopes and molecules. 28 refs., 1 fig., 1 tab.

  19. Stable isotope analysis of precipitation samples obtained via crowdsourcing reveals the spatiotemporal evolution of Superstorm Sandy.

    PubMed

    Good, Stephen P; Mallia, Derek V; Lin, John C; Bowen, Gabriel J

    2014-01-01

    Extra-tropical cyclones, such as 2012 Superstorm Sandy, pose a significant climatic threat to the northeastern United Sates, yet prediction of hydrologic and thermodynamic processes within such systems is complicated by their interaction with mid-latitude water patterns as they move poleward. Fortunately, the evolution of these systems is also recorded in the stable isotope ratios of storm-associated precipitation and water vapor, and isotopic analysis provides constraints on difficult-to-observe cyclone dynamics. During Superstorm Sandy, a unique crowdsourced approach enabled 685 precipitation samples to be obtained for oxygen and hydrogen isotopic analysis, constituting the largest isotopic sampling of a synoptic-scale system to date. Isotopically, these waters span an enormous range of values (> 21‰ for δ(18)O, > 160‰ for δ(2)H) and exhibit strong spatiotemporal structure. Low isotope ratios occurred predominantly in the west and south quadrants of the storm, indicating robust isotopic distillation that tracked the intensity of the storm's warm core. Elevated values of deuterium-excess (> 25‰) were found primarily in the New England region after Sandy made landfall. Isotope mass balance calculations and Lagrangian back-trajectory analysis suggest that these samples reflect the moistening of dry continental air entrained from a mid-latitude trough. These results demonstrate the power of rapid-response isotope monitoring to elucidate the structure and dynamics of water cycling within synoptic-scale systems and improve our understanding of storm evolution, hydroclimatological impacts, and paleo-storm proxies.

  20. Stable Isotope Analysis of Precipitation Samples Obtained via Crowdsourcing Reveals the Spatiotemporal Evolution of Superstorm Sandy

    PubMed Central

    Good, Stephen P.; Mallia, Derek V.; Lin, John C.; Bowen, Gabriel J.

    2014-01-01

    Extra-tropical cyclones, such as 2012 Superstorm Sandy, pose a significant climatic threat to the northeastern United Sates, yet prediction of hydrologic and thermodynamic processes within such systems is complicated by their interaction with mid-latitude water patterns as they move poleward. Fortunately, the evolution of these systems is also recorded in the stable isotope ratios of storm-associated precipitation and water vapor, and isotopic analysis provides constraints on difficult-to-observe cyclone dynamics. During Superstorm Sandy, a unique crowdsourced approach enabled 685 precipitation samples to be obtained for oxygen and hydrogen isotopic analysis, constituting the largest isotopic sampling of a synoptic-scale system to date. Isotopically, these waters span an enormous range of values (21‰ for O, 160‰ for H) and exhibit strong spatiotemporal structure. Low isotope ratios occurred predominantly in the west and south quadrants of the storm, indicating robust isotopic distillation that tracked the intensity of the storm's warm core. Elevated values of deuterium-excess (25‰) were found primarily in the New England region after Sandy made landfall. Isotope mass balance calculations and Lagrangian back-trajectory analysis suggest that these samples reflect the moistening of dry continental air entrained from a mid-latitude trough. These results demonstrate the power of rapid-response isotope monitoring to elucidate the structure and dynamics of water cycling within synoptic-scale systems and improve our understanding of storm evolution, hydroclimatological impacts, and paleo-storm proxies. PMID:24618882

  1. Fast and Accurate Radiative Transfer Calculations Using Principal Component Analysis for (Exo-)Planetary Retrieval Models

    NASA Astrophysics Data System (ADS)

    Kopparla, P.; Natraj, V.; Shia, R. L.; Spurr, R. J. D.; Crisp, D.; Yung, Y. L.

    2015-12-01

    Radiative transfer (RT) computations form the engine of atmospheric retrieval codes. However, full treatment of RT processes is computationally expensive, prompting usage of two-stream approximations in current exoplanetary atmospheric retrieval codes [Line et al., 2013]. Natraj et al. [2005, 2010] and Spurr and Natraj [2013] demonstrated the ability of a technique using principal component analysis (PCA) to speed up RT computations. In the PCA method for RT performance enhancement, empirical orthogonal functions are developed for binned sets of inherent optical properties that possess some redundancy; costly multiple-scattering RT calculations are only done for those few optical states corresponding to the most important principal components, and correction factors are applied to approximate radiation fields. Kopparla et al. [2015, in preparation] extended the PCA method to a broadband spectral region from the ultraviolet to the shortwave infrared (0.3-3 micron), accounting for major gas absorptions in this region. Here, we apply the PCA method to a some typical (exo-)planetary retrieval problems. Comparisons between the new model, called Universal Principal Component Analysis Radiative Transfer (UPCART) model, two-stream models and line-by-line RT models are performed, for spectral radiances, spectral fluxes and broadband fluxes. Each of these are calculated at the top of the atmosphere for several scenarios with varying aerosol types, extinction and scattering optical depth profiles, and stellar and viewing geometries. We demonstrate that very accurate radiance and flux estimates can be obtained, with better than 1% accuracy in all spectral regions and better than 0.1% in most cases, as compared to a numerically exact line-by-line RT model. The accuracy is enhanced when the results are convolved to typical instrument resolutions. The operational speed and accuracy of UPCART can be further improved by optimizing binning schemes and parallelizing the codes, work

  2. Accurate means of detecting and characterizing abnormal patterns of ventricular activation by phase image analysis

    SciTech Connect

    Botvinick, E.H.; Frais, M.A.; Shosa, D.W.; O'Connell, J.W.; Pacheco-Alvarez, J.A.; Scheinman, M.; Hattner, R.S.; Morady, F.; Faulkner, D.B.

    1982-08-01

    The ability of scintigraphic phase image analysis to characterize patterns of abnormal ventricular activation was investigated. The pattern of phase distribution and sequential phase changes over both right and left ventricular regions of interest were evaluated in 16 patients with normal electrical activation and wall motion and compared with those in 8 patients with an artificial pacemaker and 4 patients with sinus rhythm with the Wolff-Parkinson-White syndrome and delta waves. Normally, the site of earliest phase angle was seen at the base of the interventricular septum, with sequential change affecting the body of the septum and the cardiac apex and then spreading laterally to involve the body of both ventricles. The site of earliest phase angle was located at the apex of the right ventricle in seven patients with a right ventricular endocardial pacemaker and on the lateral left ventricular wall in one patient with a left ventricular epicardial pacemaker. In each case the site corresponded exactly to the position of the pacing electrode as seen on posteroanterior and left lateral chest X-ray films, and sequential phase changes spread from the initial focus to affect both ventricles. In each of the patients with the Wolff-Parkinson-White syndrome, the site of earliest ventricular phase angle was located, and it corresponded exactly to the site of the bypass tract as determined by endocardial mapping. In this way, four bypass pathways, two posterior left paraseptal, one left lateral and one right lateral, were correctly localized scintigraphically. On the basis of the sequence of mechanical contraction, phase image analysis provides an accurate noninvasive method of detecting abnormal foci of ventricular activation.

  3. Methods for applying accurate digital PCR analysis on low copy DNA samples.

    PubMed

    Whale, Alexandra S; Cowen, Simon; Foy, Carole A; Huggett, Jim F

    2013-01-01

    Digital PCR (dPCR) is a highly accurate molecular approach, capable of precise measurements, offering a number of unique opportunities. However, in its current format dPCR can be limited by the amount of sample that can be analysed and consequently additional considerations such as performing multiplex reactions or pre-amplification can be considered. This study investigated the impact of duplexing and pre-amplification on dPCR analysis by using three different assays targeting a model template (a portion of the Arabidopsis thaliana alcohol dehydrogenase gene). We also investigated the impact of different template types (linearised plasmid clone and more complex genomic DNA) on measurement precision using dPCR. We were able to demonstrate that duplex dPCR can provide a more precise measurement than uniplex dPCR, while applying pre-amplification or varying template type can significantly decrease the precision of dPCR. Furthermore, we also demonstrate that the pre-amplification step can introduce measurement bias that is not consistent between experiments for a sample or assay and so could not be compensated for during the analysis of this data set. We also describe a model for estimating the prevalence of molecular dropout and identify this as a source of dPCR imprecision. Our data have demonstrated that the precision afforded by dPCR at low sample concentration can exceed that of the same template post pre-amplification thereby negating the need for this additional step. Our findings also highlight the technical differences between different templates types containing the same sequence that must be considered if plasmid DNA is to be used to assess or control for more complex templates like genomic DNA.

  4. Hanford isotope project strategic business analysis yttrium-90 (Y-90)

    SciTech Connect

    1995-10-01

    The purpose of this analysis is to address the short-term direction for the Hanford yttrium-90 (Y-90) project. Hanford is the sole DOE producer of Y-90, and is the largest repository for its source in this country. The production of Y-90 is part of the DOE Isotope Production and Distribution (IP and D) mission. The Y-90 is ``milked`` from strontium-90 (Sr-90), a byproduct of the previous Hanford missions. The use of Sr-90 to produce Y-90 could help reduce the amount of waste material processed and the related costs incurred by the clean-up mission, while providing medical and economic benefits. The cost of producing Y-90 is being subsidized by DOE-IP and D due to its use for research, and resultant low production level. It is possible that the sales of Y-90 could produce full cost recovery within two to three years, at two curies per week. Preliminary projections place the demand at between 20,000 and 50,000 curies per year within the next ten years, assuming FDA approval of one or more of the current therapies now in clinical trials. This level of production would incentivize private firms to commercialize the operation, and allow the government to recover some of its sunk costs. There are a number of potential barriers to the success of the Y-90 project, outside the control of the Hanford Site. The key issues include: efficacy, Food and Drug Administration (FDA) approval and medical community acceptance. There are at least three other sources for Y-90 available to the US users, but they appear to have limited resources to produce the isotope. Several companies have communicated interest in entering into agreements with Hanford for the processing and distribution of Y-90, including some of the major pharmaceutical firms in this country.

  5. Biometrics from the carbon isotope ratio analysis of amino acids in human hair.

    PubMed

    Jackson, Glen P; An, Yan; Konstantynova, Kateryna I; Rashaid, Ayat H B

    2015-01-01

    This study compares and contrasts the ability to classify individuals into different grouping factors through either bulk isotope ratio analysis or amino-acid-specific isotope ratio analysis of human hair. Using LC-IRMS, we measured the isotope ratios of 14 amino acids in hair proteins independently, and leucine/isoleucine as a co-eluting pair, to provide 15 variables for classification. Multivariate analysis confirmed that the essential amino acids and non-essential amino acids were mostly independent variables in the classification rules, thereby enabling the separation of dietary factors of isotope intake from intrinsic or phenotypic factors of isotope fractionation. Multivariate analysis revealed at least two potential sources of non-dietary factors influencing the carbon isotope ratio values of the amino acids in human hair: body mass index (BMI) and age. These results provide evidence that compound-specific isotope ratio analysis has the potential to go beyond region-of-origin or geospatial movements of individuals-obtainable through bulk isotope measurements-to the provision of physical and characteristic traits about the individuals, such as age and BMI. Further development and refinement, for example to genetic, metabolic, disease and hormonal factors could ultimately be of great assistance in forensic and clinical casework.

  6. Multi element (C, H, O) stable isotope analysis for the authentication of balsamic vinegars.

    PubMed

    Werner, Roland A; Roßmann, Andreas

    2015-01-01

    Balsamic vinegars are important and well-acknowledged products and have become more important all over Europe during the recent past. For their analytical control, stable isotope methods play an important role to check the authenticity of the raw materials applied. For vinegar, but not yet for balsamic vinegar analysis, stable isotope methods using hydrogen, carbon, and oxygen isotope analyses by isotope ratio mass spectrometry and (2)H-NMR have already been introduced as official methods. Nevertheless, the official procedure can be also applied for balsamic vinegars. The evaluation of the stable isotope parameters obtained for the ingredients of balsamic vinegars requires a knowledge and understanding of the natural and industrial processes on which the production of balsamic vinegars is based. Ranges and 'cut-off' values for the multi element stable isotope parameters of balsamic vinegars are described, and a suitable analytical strategy is suggested.

  7. Isotope Enrichment Detection by Laser Ablation - Laser Absorption Spectrometry: Automated Environmental Sampling and Laser-Based Analysis for HEU Detection

    SciTech Connect

    Anheier, Norman C.; Bushaw, Bruce A.

    2010-01-01

    The global expansion of nuclear power, and consequently the uranium enrichment industry, requires the development of new safeguards technology to mitigate proliferation risks. Current enrichment monitoring instruments exist that provide only yes/no detection of highly enriched uranium (HEU) production. More accurate accountancy measurements are typically restricted to gamma-ray and weight measurements taken in cylinder storage yards. Analysis of environmental and cylinder content samples have much higher effectiveness, but this approach requires onsite sampling, shipping, and time-consuming laboratory analysis and reporting. Given that large modern gaseous centrifuge enrichment plants (GCEPs) can quickly produce a significant quantity (SQ ) of HEU, these limitations in verification suggest the need for more timely detection of potential facility misuse. The Pacific Northwest National Laboratory (PNNL) is developing an unattended safeguards instrument concept, combining continuous aerosol particulate collection with uranium isotope assay, to provide timely analysis of enrichment levels within low enriched uranium facilities. This approach is based on laser vaporization of aerosol particulate samples, followed by wavelength tuned laser diode spectroscopy to characterize the uranium isotopic ratio through subtle differences in atomic absorption wavelengths. Environmental sampling (ES) media from an integrated aerosol collector is introduced into a small, reduced pressure chamber, where a focused pulsed laser vaporizes material from a 10 to 20-µm diameter spot of the surface of the sampling media. The plume of ejected material begins as high-temperature plasma that yields ions and atoms, as well as molecules and molecular ions. We concentrate on the plume of atomic vapor that remains after the plasma has expanded and then cooled by the surrounding cover gas. Tunable diode lasers are directed through this plume and each isotope is detected by monitoring absorbance

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

    EPA Science Inventory

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

  9. Analysis of sequential reactive transformations using stable isotope analysis: a theoretical assessment

    NASA Astrophysics Data System (ADS)

    Thullner, Martin; Jin, Shuang; Stadler, Susanne

    2016-04-01

    Stable isotope methods have been establish as powerful tools for the analysis of reactive transformation in the subsurface with applications ranging from the field of contaminant hydrology to biogeochemical cycling. While the link between single transformations based on stable isotope signatures and their changes is commonly well understood and allows for qualitative and - in case certain requirements are met - also quantitative analysis, the interpretation of sequential reactive transformations, e.g. decay chains, is more complicated. In the latter case isotope signature changes of individual reactive compounds are affected by more than one transformation which challenges the interpretation of these changes. In recent years, some methods have been proposed (e.g. isotope mass balance approaches) which allow at least for a qualitative or semi-quantitative estimation of sequential reactive transformation processes. However, a systematic assessment of the validity of these estimation methods is missing so far and the accuracy of these methods - in general and for specific conditions encountered in the field - is not fully validated. In this presentation we use a combination of mathematical analyses and numerical modeling to test the validity of the proposed estimation methods and to determine the limits of their applicability. Results recommend modifications of existing theoretical estimation approaches and identify sorption processes as potential limitation of their applicability.

  10. Accurate mass fragment library for rapid analysis of pesticides on produce using ambient pressure desorption ionization with high-resolution mass spectrometry.

    PubMed

    Kern, Sara E; Lin, Lora A; Fricke, Frederick L

    2014-08-01

    U.S. food imports have been increasing steadily for decades, intensifying the need for a rapid and sensitive screening technique. A method has been developed that uses foam disks to sample the surface of incoming produce. This work provides complimentary information to the extensive amount of published pesticide fragmentation data collected using LCMS systems (Sack et al. Journal of Agricultural and Food Chemistry, 59, 6383-6411, 2011; Mol et al. Analytical and Bioanalytical Chemistry, 403, 2891-2908, 2012). The disks are directly analyzed using transmission-mode direct analysis in real time (DART) ambient pressure desorption ionization coupled to a high resolution accurate mass-mass spectrometer (HRAM-MS). In order to provide more certainty in the identification of the pesticides detected, a library of accurate mass fragments and isotopes of the protonated parent molecular ion (the [M+H]⁺) has been developed. The HRAM-MS is equipped with a quadrupole mass filter, providing the capability of "data-dependent" fragmentation, as opposed to "all -ion" fragmentation (where all of the ions enter a collision chamber and are fragmented at once). A temperature gradient for the DART helium stream and multiple collision energies were employed to detect and fragment 164 pesticides of varying chemical classes, sizes, and polarities. The accurate mass information of precursor ([M+H]⁺ ion) and fragment ions is essential in correctly identifying chemical contaminants on the surface of imported produce. Additionally, the inclusion of isotopes of the [M+H]⁺ in the database adds another metric to the confirmation process. The fragmentation data were collected using a Q-Exactive mass spectrometer and were added to a database used to process data collected with an Exactive mass spectrometer, an instrument that is more readily available for this screening application. The commodities investigated range from smooth-skinned produce such as apples to rougher surfaces like broccoli

  11. Accurate Mass Fragment Library for Rapid Analysis of Pesticides on Produce Using Ambient Pressure Desorption Ionization with High-Resolution Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Kern, Sara E.; Lin, Lora A.; Fricke, Frederick L.

    2014-08-01

    U.S. food imports have been increasing steadily for decades, intensifying the need for a rapid and sensitive screening technique. A method has been developed that uses foam disks to sample the surface of incoming produce. This work provides complimentary information to the extensive amount of published pesticide fragmentation data collected using LCMS systems (Sack et al. Journal of Agricultural and Food Chemistry, 59, 6383-6411, 2011; Mol et al. Analytical and Bioanalytical Chemistry, 403, 2891-2908, 2012). The disks are directly analyzed using transmission-mode direct analysis in real time (DART) ambient pressure desorption ionization coupled to a high resolution accurate mass-mass spectrometer (HRAM-MS). In order to provide more certainty in the identification of the pesticides detected, a library of accurate mass fragments and isotopes of the protonated parent molecular ion (the [M+H]+) has been developed. The HRAM-MS is equipped with a quadrupole mass filter, providing the capability of "data-dependent" fragmentation, as opposed to "all -ion" fragmentation (where all of the ions enter a collision chamber and are fragmented at once). A temperature gradient for the DART helium stream and multiple collision energies were employed to detect and fragment 164 pesticides of varying chemical classes, sizes, and polarities. The accurate mass information of precursor ([M+H]+ ion) and fragment ions is essential in correctly identifying chemical contaminants on the surface of imported produce. Additionally, the inclusion of isotopes of the [M+H]+ in the database adds another metric to the confirmation process. The fragmentation data were collected using a Q-Exactive mass spectrometer and were added to a database used to process data collected with an Exactive mass spectrometer, an instrument that is more readily available for this screening application. The commodities investigated range from smooth-skinned produce such as apples to rougher surfaces like broccoli. The

  12. Dissolution of barite for the analysis of strontium isotopes and other chemical and isotopic variations using aqueous sodium carbonate

    USGS Publications Warehouse

    Breit, G.N.; Simmons, E.C.; Goldhaber, M.B.

    1985-01-01

    A simple procedure for preparing barite samples for chemical and isotopic analysis is described. Sulfate ion, in barite, in the presence of high concentrations of aqueous sodium carbonate, is replaced by carbonate. This replacement forms insoluble carbonates with the cations commonly in barite: Ba, Sr, Ca and Pb. Sulfate is released into the solution by the carbonate replacement and is separated by filtration. The aqueous sulfate can then be reprecipitated for analysis of the sulfur and oxygen isotopes. The cations in the carbonate phase can be dissolved by acidifying the solid residue. Sr can be separated from the solution for Sr isotope analysis by ion-exchange chromatography. The sodium carbonate used contains amounts of Sr which will affect almost all barite 87Sr 86Sr ratios by less than 0.00001 at 1.95?? of the mean. The procedure is preferred over other techniques used for preparing barite samples for the determination of 87Sr 86Sr ratios because it is simple, rapid and enables simultaneous determination of many compositional parameters on the same material. ?? 1985.

  13. In Situ Analysis of Organics and Isotopes at Mars

    NASA Astrophysics Data System (ADS)

    Mahaffy, P. R.; Atreya, S. K.; Brinckerhoff, W. B.; Cabane, M.; Coll, P.; Demick, J.; Harpold, D. N.; Ming, D.; Niemann, H.; Owen, T.; Raulin, F.; Scott, J.; Webster, C.

    2003-05-01

    The recent success of the "follow the water" imperative for Mars exploration is tempered by the fact that more than 2 decades after Viking, much remains unknown about the state of carbon at the planet's surface. Therefore, a key objective for lander missions that follow MER will be a search for the location and nature of organic molecules and other carbon containing species. Reduced or partially oxidized compounds may reveal the nature of ancient or even present biotic or prebiotic processes. Ongoing definition and development of advanced techniques and protocols to "follow the carbon" will be described. For example, an instrument suite presently under development to be proposed for inclusion on the 2009 Mars Science Laboratory consists of an advanced gas chromatograph mass spectrometer (GCMS) with derivatization capability coupled with a laser desorption time-of-flight mass spectrometer (LDMS) and a tunable laser spectrometer (TLS). The suite is designated SAM (for Sample Analysis at Mars) and is designed to carry out analysis of both atmospheric gases and volatiles released from solid phase soils, rock samples, and ices. Volatile organic molecules and their pyrolysis products are analyzed by the GCMS and TLS, and refractory organics and elements by the LDMS. Additional objectives include higher precision measurements than have been obtained, to date, of the abundances and isotope ratios of the noble gases and a range of light elements including H, C, O, and N in both the atmosphere and soil. SAM can also contribute to geochemical objectives with the identification of various minerals through evolved gas analysis (EGA) of stable thermal decomposition products such as H2O, CO2, and oxides of nitrogen and sulfur using the MS and TLS as the detector. Recent EGA studies on Mars analogue materials that illustrate this capability are described. This work is supported by funding from NASA and CNES

  14. Direct analysis of air filter samples for alpha emitting isotopes

    SciTech Connect

    Mohagheghi, A.H.; Ghanbari, F.; Ebara, S.B.; Enghauser, M.E.; Bakhtiar, S.N.

    1997-04-01

    The traditional method for determination of alpha emitting isotopes on air filters has been to process the samples by radiochemical methods. However, this method is too slow for cases of incidents involving radioactive materials where the determination of personnel received dose is urgent. A method is developed to directly analyze the air filters taken from personal and area air monitors. The site knowledge is used in combination with alpha spectral information to identify isotopes. A mathematical function is developed to estimate the activity for each isotope. The strengths and weaknesses of the method are discussed.

  15. Laboratory and field methods for stable isotope analysis in human biology.

    PubMed

    Reitsema, Laurie J

    2015-01-01

    Stable isotope analysis (SIA; carbon, hydrogen, nitrogen, sulfur, and oxygen) of human tissues offers a means for assessing diet among living humans. Stable isotope ratios of broad categories of food and drink food vary systematically, and stable isotope ratios in consumer tissues represent a composite of the isotopic ratios of food and drink consumed during an individual's life. Isotopic evidence for diet is independent of errors in informant recall, and accrues during time periods when researchers are absent. Beyond diet reconstruction, tissue stable isotope ratios are sensitive to excursions from homeostasis, such as starvation and rapid growth. Because of their relationship to diet, geographic location, hydration, and nutritional status, stable isotope signatures in human tissues offer a window into human biocultural adaptations, past and present. This article describes methods for SIA that may be usefully applied in studies of living humans, with emphasis placed on carbon and nitrogen. Some of the ecological, physiological, and evolutionary applications of stable isotope data among living humans are discussed. By incorporating SIA in research, human biologists facilitate a productive dialog with bioarchaeologists, who routinely use stable isotope evidence, mingling different perspectives on human biology and behavior.

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

    USGS Publications Warehouse

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

    2012-01-01

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

  17. Applications, considerations, and sources of uncertainty when using stable isotope analysis in ecotoxicology.

    PubMed

    Jardine, Timothy D; Kidd, Karen A; Fisk, Aaron T

    2006-12-15

    Stable isotope analysis (SIA) has become a powerful tool for ecotoxicologists to study dietary exposure and biomagnification of contaminants in wild animal populations. The use of SIA in ecotoxicology continues to expand and, while much more is known about the mechanisms driving patterns of isotopic ratios in consumers, there remain several considerations or sources of uncertainty that can influence interpretation of data from field studies. We outline current uses of SIA in ecotoxicology, including estimating the importance of dietary sources of carbon and their application in biomagnification studies, and we present six main considerations or sources of uncertainty associated with the approach: (1) unequal diet-tissue stable isotope fractionation among species, (2) variable diet-tissue stable isotope fractionation within a given species, (3) different stable isotope ratios in different tissues of the animal, (4) fluctuating baseline stable isotope ratios across systems, (5) the presence of true omnivores, and (6) movement of animals and nutrients between food webs. Since these considerations or sources of uncertainty are difficult to assess in field studies, we advocate that researchers consider the following in designing ecotoxicological research and interpreting results: assess and utilize variation in stable isotope diet-tissue fractionation among animal groups available in the literature; determine stable isotope ratios in multiple tissues to provide a temporal assessment of feeding; adequately characterize baseline isotope ratios; utilize stomach contents when possible; and assess and integrate life history of study animals in a system.

  18. Sensitivity analysis and quantification of uncertainty for isotopic mixing relationships in carbon cycle research

    NASA Astrophysics Data System (ADS)

    Zobitz, J. M.; Keener, J. P.; Bowling, D. R.

    2004-12-01

    Quantifying and understanding the uncertainty in isotopic mixing relationships is critical to isotopic applications in carbon cycle studies at all spatial and temporal scales. Studies associated with the North American Carbon Program will depend on stable isotope approaches and quantification of isotopic uncertainty. An important application of isotopic mixing relationships is determination of the isotopic content of large-scale respiration (δ 13CR) via an inverse relationship (a Keeling plot) between atmospheric CO2 concentrations ([CO2]) and carbon isotope ratios of CO2 (δ 13C). Alternatively, a linear relationship between [CO2] and the product of [CO2] and δ 13C (a Miller/Tans plot) can also be applied. We used an extensive dataset from the Niwot Ridge Ameriflux Site of [CO2] and δ 13C in forest air to examine contrasting approaches to determine δ 13CR and its uncertainty. These included Keeling plots, Miller/Tans plots, Model I, and Model II regressions Our analysis confirms previous observations that increasing the range of measurements ([CO2] range) reduces the uncertainty associated with δ 13CR. For carbon isotope studies, uncertainty in the isotopic measurements has a greater effect on the uncertainty of δ 13CR than the uncertainty in [CO2]. Reducing the uncertainty of isotopic measurements reduces the uncertainty of δ 13CR even when the [CO2] range of samples is small (< 20 ppm). As a result, improvement in isotope (rather than CO2) measuring capability is needed to substantially reduce uncertainty in δ 13CR. We also find for carbon isotope studies no inherent advantage to using either a Keeling or a Miller/Tans approach to determine δ 13CR.

  19. Accurate Free Vibration Analysis of the Completely Free Rectangular Mindlin Plate

    NASA Astrophysics Data System (ADS)

    Gorman, D. J.; Ding, Wei

    1996-01-01

    The superposition method is exploited to obtain accurate solutions for the natural frequencies and mode shapes of the completely free Mindlin plate. Computed eigenvalues are tabulated for a number of plate aspect and thickness ratios. Steps taken to avoid computational instability are described. Difficulties associated with choosing mode shape functions, particularly when free edges are involved, have always hindered researchers utilizing the Rayleigh-Ritz method. Such difficulties are obviated here. To the authors' knowledge, this represents the first accurate comprehensive solution to this important plate vibration problem.

  20. 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.

  1. Carbon Stable Isotope Analysis of Methylmercury Toxin in Biological Materials by Gas Chromatography Isotope Ratio Mass Spectrometry.

    PubMed

    Masbou, Jeremy; Point, David; Guillou, Gaël; Sonke, Jeroen E; Lebreton, Benoit; Richard, Pierre

    2015-12-01

    A critical component of the biogeochemical cycle of mercury (Hg) is the transformation of inorganic Hg to neurotoxic monomethylmercury (CH3Hg). Humans are exposed to CH3Hg by consuming marine fish, yet the origin of CH3Hg in fish is a topic of debate. The carbon stable isotopic composition (δ(13)C) embedded in the methyl group of CH3Hg remains unexplored. This new isotopic information at the molecular level is thought to represent a new proxy to trace the carbon source at the origin of CH3Hg. Here, we present a compound-specific stable isotope analysis (CSIA) technique for the determination of the δ(13)C value of CH3Hg in biological samples by gas chromatography combustion isotope ratio mass spectrometry analysis (GC-C-IRMS). The method consists first of calibrating a CH3Hg standard solution for δ(13)C CSIA. This was achieved by comparing three independent approaches consisting of the derivatization and halogenation of the CH3Hg standard solution. The determination of δ(13)C(CH3Hg) values on natural biological samples was performed by combining a CH3Hg selective extraction, purification, and halogenation followed by GC-C-IRMS analysis. Reference δ(13)C values were established for a tuna fish certified material (ERM-CE464) originating from the Adriatic Sea (δ(13)C(CH3Hg) = -22.1 ± 1.5‰, ± 2 SD). This value is similar to the δ(13)C value of marine algal-derived particulate organic carbon (δ(13)CPOC = -21‰).

  2. Carbon Stable Isotope Analysis of Methylmercury Toxin in Biological Materials by Gas Chromatography Isotope Ratio Mass Spectrometry.

    PubMed

    Masbou, Jeremy; Point, David; Guillou, Gaël; Sonke, Jeroen E; Lebreton, Benoit; Richard, Pierre

    2015-12-01

    A critical component of the biogeochemical cycle of mercury (Hg) is the transformation of inorganic Hg to neurotoxic monomethylmercury (CH3Hg). Humans are exposed to CH3Hg by consuming marine fish, yet the origin of CH3Hg in fish is a topic of debate. The carbon stable isotopic composition (δ(13)C) embedded in the methyl group of CH3Hg remains unexplored. This new isotopic information at the molecular level is thought to represent a new proxy to trace the carbon source at the origin of CH3Hg. Here, we present a compound-specific stable isotope analysis (CSIA) technique for the determination of the δ(13)C value of CH3Hg in biological samples by gas chromatography combustion isotope ratio mass spectrometry analysis (GC-C-IRMS). The method consists first of calibrating a CH3Hg standard solution for δ(13)C CSIA. This was achieved by comparing three independent approaches consisting of the derivatization and halogenation of the CH3Hg standard solution. The determination of δ(13)C(CH3Hg) values on natural biological samples was performed by combining a CH3Hg selective extraction, purification, and halogenation followed by GC-C-IRMS analysis. Reference δ(13)C values were established for a tuna fish certified material (ERM-CE464) originating from the Adriatic Sea (δ(13)C(CH3Hg) = -22.1 ± 1.5‰, ± 2 SD). This value is similar to the δ(13)C value of marine algal-derived particulate organic carbon (δ(13)CPOC = -21‰). PMID:26511394

  3. Cu isotope fractionation during bornite dissolution: An in situ X-ray diffraction analysis

    SciTech Connect

    Wall, Andrew J.; Mathur, Ryan; Post, Jeffrey E.; Heaney, Peter J.

    2012-10-24

    Low-temperature ore deposits exhibit a large variation in {delta}{sup 65}Cu ({approx}12{per_thousand}), and this range has been attributed, in part, to isotope fractionation during weathering reactions of primary minerals such as chalcocite and chalcopyrite. Here, we examine the fractionation of Cu isotopes during dissolution of another important Cu ore mineral, bornite, using a novel approach that combines time-resolved X-ray diffraction (XRD) and isotope analysis of reaction products. During the initial stages of bornite oxidative dissolution by ferric sulfate (< 5 mol% of total Cu leached), dissolved Cu was enriched in isotopically heavy Cu ({sup 65}Cu) relative to the solid, with an average apparent isotope fractionation ({Delta}{sub aq - min} = {delta}{sup 65}Cu{sub aq} - {delta}{sup 65}Cu{sub min}{sup 0}) of 2.20 {+-} 0.25{per_thousand}. When > 20 mol% Cu was leached from the solid, the difference between the Cu isotope composition of the aqueous and mineral phases approached zero, with {Delta}{sub aq - min}{sup 0} values ranging from - 0.21 {+-} 0.61{per_thousand} to 0.92 {+-} 0.25{per_thousand}. XRD analysis allowed us to correlate changes in the atomic structure of bornite with the apparent isotope fractionation as the dissolution reaction progressed. These data revealed that the greatest degree of apparent fractionation is accompanied by a steep contraction in the unit-cell volume, which we identified as a transition from stoichiometric to non-stoichiometric bornite. We propose that the initially high {Delta}{sub aq - min} values result from isotopically heavy Cu ({sup 65}Cu) concentrating within Cu{sup 2+} during dissolution. The decrease in the apparent isotope fractionation as the reaction progresses occurs from the distillation of isotopically heavy Cu ({sup 65}Cu) during dissolution or kinetic isotope effects associated with the depletion of Cu from the surfaces of bornite particles.

  4. Computer Analysis of Isotope Clusters in Mass Spectrometry

    ERIC Educational Resources Information Center

    Bell, Harold M.

    1974-01-01

    Describes the application of a computer program designed to produce a formula determination simultaneously accounting for both elemental composition and probable isotopic species for a measured ion mass. (SLH)

  5. GUM Analysis for TIMS and SIMS Isotopic Ratios in Graphite

    SciTech Connect

    Heasler, Patrick G.; Gerlach, David C.; Cliff, John B.; Petersen, Steven L.

    2007-04-01

    This report describes GUM calculations for TIMS and SIMS isotopic ratio measurements of reactor graphite samples. These isotopic ratios are used to estimate reactor burn-up, and currently consist of various ratios of U, Pu, and Boron impurities in the graphite samples. The GUM calculation is a propagation of error methodology that assigns uncertainties (in the form of standard error and confidence bound) to the final estimates.

  6. Oceanic and Climate phasing analysis across Marine Isotope Stage 3

    NASA Astrophysics Data System (ADS)

    Henry, G., III; McManus, J. F.; Curry, W. B.; Roberts, N. L.; Piotrowski, A. M.; Keigwin, L. D.

    2015-12-01

    Glacial climate oscillated between cold stadial periods similar to the Last Glacial Maximum and warmer periods more similar to today from 25,000 to 60,000 years BP, an envelop of time referred to as marine isotope stage three (MIS3). The sudden warmings (Dansgaard-Oeschger events) and ice sheet surges (Heinrich events) have long captured researchers' attention as a means of exploring significant perturbations to the climate system. The climate dynamics associated with these events have been recently elucidated throughhigh-resolution analysis of ice and sediment core archives. In particular, it has been recently demonstrated through synchronization of Greenlandic and Antarctic ice cores that abrupt climate events propagated from the Northern to Southern hemisphere. Likewise, during Heinrich events ice rafted detritus appeared in the Northern North Atlantic generally after cold stadial conditions had already been established. These results indict the ocean's conveyor as the vehicle hemispheric partitioning heat across these events. Here we test the phased response of multiple paleoproxies sensitive to circulation across these abrupt climate events through all of MIS3. Through correlation analysis of multiple paleoproxy records generated from a high accumulation sediment core taken from the Bermuda Rise, we examine the phase relationship of high latitude climate records with the kinematic circulation proxy Pa/Th, benthic d13C and d18O, SST, d18Osw, CaCO3 content, 230Th-normalized bulk and component fluxes in order to infer the sequence of change across these abrupt millennial events. We find that shifts in water mass composition precede increases in temperatures across the identified time interval, while the export of Pa relative to Th increases in tandem with changes in with Bermuda Rise SST estimates during warmings, but lags during cooling. Rapid shifts in thorium normalized carbonate flux supply secondary evidence for changes in preservation accompanying changes

  7. Analysis of Hydrogen Isotopic Exchange: Lava Creek Tuff Ash and Isotopically Labeled Water

    NASA Astrophysics Data System (ADS)

    Ross, A. M.; Seligman, A. N.; Bindeman, I. N.; Nolan, G. S.

    2015-12-01

    Nolan and Bindeman (2013) placed secondarily hydrated ash from the 7.7 ka eruption of Mt. Mazama (δD=-149‰, 2.3wt% H2Ot) in isotopically labeled water (+650 ‰ δD, +56 ‰ δ18O) and observed that the H2Ot and δ18O values remained constant, but the δD values of ash increased with the surrounding water at 20, 40 and 70 °C. We expand on this work by conducting a similar experiment with ash from the 640 ka Lava Creek Tuff (LCT, δD of -128 ‰; 2.1 wt.% H2Ot) eruption of Yellowstone to see if significantly older glass (with a hypothesized gel layer on the surface shielding the interior from alteration) produces the same results. We have experiments running at 70, 24, and 5 °C, and periodically remove ~1.5 mg of glass to measure the δD (‰) and H2Ot (wt.%) of water extracted from the glass on a TC/EA MAT 253 continuous flow system. After 600 hours, the δD of the samples left at 5 and 24 °C remains at -128 ‰, but increased 8‰ for the 70 °C run series. However, there is no measurable change in wt.% of H2Ot, indicating that hydrogen exchange is not dictated by the addition of water. We are measuring and will report further progress of isotope exchange. We also plan to analyze the water in the LCT glass for δ18O (‰) to see if, as is the case for the Mt. Mazama glass, the δ18O (‰) remains constant. We also analyzed Mt. Mazama glass from the Nolan and Bindeman (2013) experiments that have now been sitting in isotopically labeled water at room temperature for ~5 years. The water concentration is still unchanged (2.3 wt.% H2Ot), and the δD of the water in the glass is now -111 ‰, causing an increase of 38 ‰. Our preliminary results show that exchange of hydrogen isotopes of hydrated glass is not limited by the age of the glass, and that the testing of hydrogen isotopes of secondarily hydrated glass, regardless of age, may not be a reliable paleoclimate indicator.

  8. Isotope fractionation studies of molybdenum

    NASA Astrophysics Data System (ADS)

    Wieser, M. E.; de Laeter, J. R.; Varner, M. D.

    2007-08-01

    Mass spectrometric studies of the isotopic composition of molybdenum have become an active area of research in stable isotope geochemistry, biogeochemistry and cosmochemistry. The redox chemistry of Mo, together with its proclivity for covalent bonding, indicates its importance in isotope fractionation studies such as palaeoceanography. The measurement of the magnitude of isotope fractionation of Mo in natural systems is a challenging task, in that natural fractionation has to be carefully distinguished from chemical and instrumental isotope fractionation. An ion exchange chemical separation procedure has been developed with high efficiency and low blank, to ensure that the isobaric elements Zr and Ru are removed from the samples before mass spectrometric analysis. The isotope fractionation resulting from this procedure is 0.14[per mille sign] per u. The isotopic composition of Mo of a Laboratory Standard has been measured by positive and negative thermal ionization mass spectrometry (P-TIMS and N-TIMS, respectively), to give an isotope fractionation of 6.4[per mille sign] and 0.5[per mille sign] per u, respectively, with respect to the absolute isotope abundances of Mo. In both cases the lighter isotopes are enhanced with respect to the heavier isotopes. An ascorbic acid activator has enabled the sensitivity of P-TIMS to be improved as compared to traditional methods. The same experiment was repeated using a multiple collector-inductively coupled plasma-mass spectrometer (MC-ICP-MS) to give an isotope fractionation of approximately 17.0[per mille sign] per u. In this case the heavier isotopes are enhanced with respect to the lighter isotopes. The strengths and weaknesses of these three mass spectrometric techniques are evaluated. We conclude that MC-ICP-MS is the optimum mass spectrometric method for accurately measuring the isotope fractionation of Mo in natural materials, provided chemical and instrumental isotope fractionation can be resolved from naturally

  9. Internal correction of hafnium oxide spectral interferences and mass bias in the determination of platinum in environmental samples using isotope dilution analysis.

    PubMed

    Rodríguez-Castrillón, José Angel; Moldovan, Mariella; García Alonso, J Ignacio

    2009-05-01

    A method has been developed for the accurate determination of platinum by isotope dilution analysis, using enriched (194)Pt, in environmental samples containing comparatively high levels of hafnium without any chemical separation. The method is based on the computation of the contribution of hafnium oxide as an independent factor in the observed isotope pattern of platinum in the spiked sample. Under these conditions, the ratio of molar fractions between natural abundance and isotopically enriched platinum was independent of the amount of hafnium present in the sample. Additionally, mass bias was corrected by an internal procedure in which the regression variance was minimised. This was possible as the mass bias factor for hafnium oxide was very close to that of platinum. The final procedure required the measurement of three platinum isotope ratios (192/194, 195/194 and 196/194) to calculate the concentration of platinum in the sample. The methodology has been validated using the reference material "BCR-723 road dust" and has been applied to different environmental matrices (road dust, air particles, bulk wet deposition and epiphytic lichens) collected in the Aspe Valley (Pyrenees Mountains). A full uncertainty budget, using Kragten's spreadsheet method, showed that the total uncertainty was limited only by the uncertainty in the measured isotope ratios and not by the uncertainties of the isotopic composition of platinum and hafnium.

  10. Simultaneous measurement in mass and mass/mass mode for accurate qualitative and quantitative screening analysis of pharmaceuticals in river water.

    PubMed

    Martínez Bueno, M J; Ulaszewska, Maria M; Gomez, M J; Hernando, M D; Fernández-Alba, A R

    2012-09-21

    A new approach for the analysis of pharmaceuticals (target and non-target) in water by LC-QTOF-MS is described in this work. The study has been designed to assess the performance of the simultaneous quantitative screening of target compounds, and the qualitative analysis of non-target analytes, in just one run. The features of accurate mass full scan mass spectrometry together with high MS/MS spectral acquisition rates - by means of information dependent acquisition (IDA) - have demonstrated their potential application in this work. Applying this analytical strategy, an identification procedure is presented based on library searching for compounds which were not included a priori in the analytical method as target compounds, thus allowing their characterization by data processing of accurate mass measurements in MS and MS/MS mode. The non-target compounds identified in river water samples were ketorolac, trazodone, fluconazole, metformin and venlafaxine. Simultaneously, this strategy allowed for the identification of other compounds which were not included in the library by screening the highest intensity peaks detected in the samples and by analysis of the full scan TOF-MS, isotope pattern and MS/MS spectra - the example of loratadine (histaminergic) is described. The group of drugs of abuse selected as target compounds for evaluation included analgesics, opioids and psychostimulants. Satisfactory results regarding sensitivity and linearity of the developed method were obtained. Limits of detection for the selected target compounds were from 0.003 to 0.01 μg/L and 0.01 to 0.5 μg/L, in MS and MS/MS mode, respectively - by direct sample injection of 100 μL.

  11. Characterization of phenol and cresol biodegradation by compound-specific stable isotope analysis.

    PubMed

    Wei, Xi; Gilevska, Tetyana; Wetzig, Felix; Dorer, Conrad; Richnow, Hans-Hermann; Vogt, Carsten

    2016-03-01

    Microbial degradation of phenol and cresols can occur under oxic and anoxic conditions by different degradation pathways. One recent technique to take insight into reaction mechanisms is compound-specific isotope analysis (CSIA). While enzymes and reaction mechanisms of several degradation pathways have been characterized in (bio)chemical studies, associated isotope fractionation patterns have been rarely reported, possibly due to constraints in current analytical methods. In this study, carbon enrichment factors and apparent kinetic isotope effects (AKIEc) of the initial steps of different aerobic and anaerobic phenol and cresols degradation pathways were analyzed by isotope ratio mass spectrometry connected with liquid chromatography (LC-IRMS). Significant isotope fractionation was detected for aerobic ring hydroxylation, anoxic side chain hydroxylation, and anoxic fumarate addition, while anoxic carboxylation reactions produced small and inconsistent fractionation. The results suggest that several microbial degradation pathways of phenol and cresols are detectable in the environment by CSIA.

  12. Development of isotope dilution gamma-ray spectrometry for plutonium analysis

    SciTech Connect

    Li, T.K.; Parker, J.L. ); Kuno, Y.; Sato, S.; Kurosawa, A.; Akiyama, T. )

    1991-01-01

    We are studying the feasibility of determining the plutonium concentration and isotopic distribution of highly radioactive, spent-fuel dissolver solutions by employing high-resolution gamma-ray spectrometry. The study involves gamma-ray plutonium isotopic analysis for both dissolver and spiked dissolver solution samples, after plutonium is eluted through an ion-exchange column and absorbed in a small resin bead bag. The spike is well characterized, dry plutonium containing {approximately}98% of {sup 239}Pu. By using measured isotopic information, the concentration of elemental plutonium in the dissolver solution can be determined. Both the plutonium concentration and the isotopic composition of the dissolver solution obtained from this study agree well with values obtained by traditional isotope dilution mass spectrometry (IDMS). Because it is rapid, easy to operate and maintain, and costs less, this new technique could be an alternative method to IDMS for input accountability and verification measurements in reprocessing plants. 7 refs., 4 figs., 4 tabs.

  13. Application of stable isotope ratio analysis for biodegradation monitoring in groundwater.

    PubMed

    Hatzinger, Paul B; Böhlke, J K; Sturchio, Neil C

    2013-06-01

    Stable isotope ratio analysis is increasingly being applied as a tool to detect, understand, and quantify biodegradation of organic and inorganic contaminants in groundwater. An important feature of this approach is that it allows degradative losses of contaminants to be distinguished from those caused by non-destructive processes such as dilution, dispersion, and sorption. Recent advances in analytical techniques, and new approaches for interpreting stable isotope data, have expanded the utility of this method while also exposing complications and ambiguities that must be considered in data interpretations. Isotopic analyses of multiple elements in a compound, and multiple compounds in the environment, are being used to distinguish biodegradative pathways by their characteristic isotope effects. Numerical models of contaminant transport, degradation pathways, and isotopic composition are improving quantitative estimates of in situ contaminant degradation rates under realistic environmental conditions. PMID:23279929

  14. Revisit to three-dimensional percolation theory: Accurate analysis for highly stretchable conductive composite materials

    PubMed Central

    Kim, Sangwoo; Choi, Seongdae; Oh, Eunho; Byun, Junghwan; Kim, Hyunjong; Lee, Byeongmoon; Lee, Seunghwan; Hong, Yongtaek

    2016-01-01

    A percolation theory based on variation of conductive filler fraction has been widely used to explain the behavior of conductive composite materials under both small and large deformation conditions. However, it typically fails in properly analyzing the materials under the large deformation since the assumption may not be valid in such a case. Therefore, we proposed a new three-dimensional percolation theory by considering three key factors: nonlinear elasticity, precisely measured strain-dependent Poisson’s ratio, and strain-dependent percolation threshold. Digital image correlation (DIC) method was used to determine actual Poisson’s ratios at various strain levels, which were used to accurately estimate variation of conductive filler volume fraction under deformation. We also adopted strain-dependent percolation threshold caused by the filler re-location with deformation. When three key factors were considered, electrical performance change was accurately analyzed for composite materials with both isotropic and anisotropic mechanical properties. PMID:27694856

  15. An Accurate Scene Segmentation Method Based on Graph Analysis Using Object Matching and Audio Feature

    NASA Astrophysics Data System (ADS)

    Yamamoto, Makoto; Haseyama, Miki

    A method for accurate scene segmentation using two kinds of directed graph obtained by object matching and audio features is proposed. Generally, in audiovisual materials, such as broadcast programs and movies, there are repeated appearances of similar shots that include frames of the same background, object or place, and such shots are included in a single scene. Many scene segmentation methods based on this idea have been proposed; however, since they use color information as visual features, they cannot provide accurate scene segmentation results if the color features change in different shots for which frames include the same object due to camera operations such as zooming and panning. In order to solve this problem, scene segmentation by the proposed method is realized by using two novel approaches. In the first approach, object matching is performed between two frames that are each included in different shots. By using these matching results, repeated appearances of shots for which frames include the same object can be successfully found and represented as a directed graph. The proposed method also generates another directed graph that represents the repeated appearances of shots with similar audio features in the second approach. By combined use of these two directed graphs, degradation of scene segmentation accuracy, which results from using only one kind of graph, can be avoided in the proposed method and thereby accurate scene segmentation can be realized. Experimental results performed by applying the proposed method to actual broadcast programs are shown to verify the effectiveness of the proposed method.

  16. The utility of accurate mass and LC elution time information in the analysis of complex proteomes

    SciTech Connect

    Norbeck, Angela D.; Monroe, Matthew E.; Adkins, Joshua N.; Anderson, Kevin K.; Daly, Don S.; Smith, Richard D.

    2005-08-01

    Theoretical tryptic digests of all predicted proteins from the genomes of three organisms of varying complexity were evaluated for specificity and possible utility of combined peptide accurate mass and predicted LC normalized elution time (NET) information. The uniqueness of each peptide was evaluated using its combined mass (+/- 5 ppm and 1 ppm) and NET value (no constraint, +/- 0.05 and 0.01 on a 0-1 NET scale). The set of peptides both underestimates actual biological complexity due to the lack of specific modifications, and overestimates the expected complexity since many proteins will not be present in the sample or observable on the mass spectrometer because of dynamic range limitations. Once a peptide is identified from an LCMS/MS experiment, its mass and elution time is representative of a unique fingerprint for that peptide. The uniqueness of that fingerprint in comparison to that for the other peptides present is indicative of the ability to confidently identify that peptide based on accurate mass and NET measurements. These measurements can be made using HPLC coupled with high resolution MS in a high-throughput manner. Results show that for organisms with comparatively small proteomes, such as Deinococcus radiodurans, modest mass and elution time accuracies are generally adequate for peptide identifications. For more complex proteomes, increasingly accurate easurements are required. However, the majority of proteins should be uniquely identifiable by using LC-MS with mass accuracies within +/- 1 ppm and elution time easurements within +/- 0.01 NET.

  17. Compound Specific Stable Isotope Analysis of Southern African Aerosols

    NASA Astrophysics Data System (ADS)

    Billmark, K. A.; Swap, R. J.; Macko, S. A.

    2001-12-01

    Southern Africa has recently been the focus of intensive subcontinental level study, particularly with regard to atmospheric aerosols and regional atmospheric transport. Results from these analyses have shown that emissions from extensive, often anthropogenic, biomass burning in southern Africa affects biogeochemical cycling in the region, and that emitted trace gases and aerosols as well as industrial emissions, marine aerosols and mineral dust tend to accumulate and recirculate in the well defined anticyclonic atmospheric gyre that persists for long time periods over southern Africa. The long-range transport of these materials is an important component of biogeochemical dynamics in this nutrient limited region. A recent field campaign, the Southern African Regional Science Initiative (SAFARI 2000), was conducted in part to investigate the impacts of this large-scale transport and deposition of aerosols on southern African biogeochemical cycling. As a part of the SAFARI 2000 initiative, we present data illustrating that compound specific stable isotope analysis of individual molecular components is a useful tool for the evaluation of the origins of aerosols and their generating processes. This study specifically examines fatty acids extracted from aerosols to more precisely characterize emissions produced in the high intensity biomass burning region of western Zambia, the slightly less intense biomass burning region of northeastern South Africa and a site downwind of these two regions within the gyre circulation at Sua Pan, Botswana. This discrete characterization of fatty acids contained within the organic fraction of collected aerosols establishes a means to trace biomass burning products as they are transported within the gyre and subsequently deposited on the subcontinent.

  18. Secondary Ionization Mass Spectrometric Analysis of Impurity Element Isotope Ratios in Nuclear Reactor Materials

    SciTech Connect

    Gerlach, David C.; Cliff, John B.; Hurley, David E.; Reid, Bruce D.; Little, Winston W.; Meriwether, George H.; Wickham, Anthony J.; Simmons, Tere A.

    2006-07-30

    Secondary ion mass spectrometry (SIMS) analysis has been used to measure isotope ratios of selected impurity elements in irradiated reactor materials. Samples of reactor materials such as graphite or aluminum alloys are obtained from fuel channels or supporting materials. During reactor operations and fuel burn up, some isotopic abundances change due to nuclear reactions and provide sensitive indicators of neutron fluence. The rate of change is related to cross section for a particular isotope. Different isotopes can be used as indicators of burn up during different stages in the reactor operating history. Isotope ratios of B are useful indicators for low burnup stages early in reactor operations, Ti isotope ratios are useful at later burn up stages, and Cl isotope ratios are useful in both early and later stages. Knowledge of the sample position within the reactor also yields information on the fluence shape or profile. In a sequence of samples from one reactor, 10B/11B ratios decreased from near natural values of 0.25 to < 0.03. Direct SIMS measurements of isotope ratios have been possible in materials, following shaping and surface cleaning trials which have included dry ice micropellet blasting, plasma etching, and vacuum furnace treatment.

  19. Study of medical isotope production facility stack emissions and noble gas isotopic signature using automatic gamma-spectra analysis platform

    NASA Astrophysics Data System (ADS)

    Zhang, Weihua; Hoffmann, Emmy; Ungar, Kurt; Dolinar, George; Miley, Harry; Mekarski, Pawel; Schrom, Brian; Hoffman, Ian; Lawrie, Ryan; Loosz, Tom

    2013-04-01

    The nuclear industry emissions of the four CTBT (Comprehensive Nuclear-Test-Ban Treaty) relevant radioxenon isotopes are unavoidably detected by the IMS along with possible treaty violations. Another civil source of radioxenon emissions which contributes to the global background is radiopharmaceutical production companies. To better understand the source terms of these background emissions, a joint project between HC, ANSTO, PNNL and CRL was formed to install real-time detection systems to support 135Xe, 133Xe, 131mXe and 133mXe measurements at the ANSTO and CRL 99Mo production facility stacks as well as the CANDU (CANada Deuterium Uranium) primary coolant monitoring system at CRL. At each site, high resolution gamma spectra were collected every 15 minutes using a HPGe detector to continuously monitor a bypass feed from the stack or CANDU primary coolant system as it passed through a sampling cell. HC also conducted atmospheric monitoring for radioxenon at approximately 200 km distant from CRL. A program was written to transfer each spectrum into a text file format suitable for the automatic gamma-spectra analysis platform and then email the file to a server. Once the email was received by the server, it was automatically analysed with the gamma-spectrum software UniSampo/Shaman to perform radionuclide identification and activity calculation for a large number of gamma-spectra in a short period of time (less than 10 seconds per spectrum). The results of nuclide activity together with other spectrum parameters were saved into the Linssi database. This database contains a large amount of radionuclide information which is a valuable resource for the analysis of radionuclide distribution within the noble gas fission product emissions. The results could be useful to identify the specific mechanisms of the activity release. The isotopic signatures of the various radioxenon species can be determined as a function of release time. Comparison of 133mXe and 133Xe activity

  20. Characterization of wines according the geographical origin by analysis of isotopes and minerals and the influence of harvest on the isotope values.

    PubMed

    Dutra, S V; Adami, L; Marcon, A R; Carnieli, G J; Roani, C A; Spinelli, F R; Leonardelli, S; Vanderlinde, R

    2013-12-01

    We studied Brazilian wines produced by microvinification from Cabernet Sauvignon and Merlot grapes, vintages 2007 and 2008, from the Serra Gaúcha, Campanha and Serra do Sudeste regions, in order to differentiate them according to geographical origin by using isotope and mineral element analyses. In addition, the influence of vintage production in isotope values was verified. Isotope analysis was performed by isotope ratio mass spectrometry (IRMS), and the determination of minerals was by flame atomic absorption (FAA). The best parameters to classify the wines in the 2008 vintage were Rb and Li. The results of the δ(13)C of wine ethanol, Rb and Li showed a significant difference between the varieties regardless of the region studied. The δ(18)O values of water and δ(13)C of ethanol showed significant differences, regardless of the variety. Discriminant analysis of isotope and minerals values allowed to classify approximately 80% of the wines from the three regions studied.

  1. Chlorine Isotopes: As a Possible Tracer of Fluid/Bio-Activities on Mars and a Progress Report on Chlorine Isotope Analysis by TIMs

    NASA Technical Reports Server (NTRS)

    Nakamura, N.; Nyquist, L.E.; Reese, Y.; Shih, C-Y.; Numata, M.; Fujitani, T.; Okano, O.

    2009-01-01

    Significantly large mass fractionations between chlorine isotopes (Cl-35, Cl-37) have been reported for terrestrial materials including both geological samples and laboratory materials. Also, the chlorine isotopic composition can be used as a tracer for early solar system processes. Moreover, chlorine is ubiquitous on the Martian surface. Typical chlorine abundances in Gusev soils are approx.0.5 %. The global surface average chlorine abundance also is approx.0.5 %. Striking variations among outcrop rocks at Meridiani were reported with some chlorine abundances as high as approx.2%. Characterizing conditions under which chlorine isotopic fractionation may occur is clearly of interest to planetary science. Thus, we have initiated development of a chlorine isotopic analysis technique using TIMS at NASA-JSC. We present here a progress report on the current status of development at JSC and discuss the possible application of chlorine isotopic analysis to Martian meteorites in a search for fluid- and possibly biological activity on Mars.

  2. Neutron Activation Analysis and Product Isotope Inventory Code System.

    1990-10-31

    Version 00 NAC was designed to predict the neutron-induced gamma-ray radioactivity for a wide variety of composite materials. The NAC output includes the input data, a list of all reactions for each constituent element, and the end-of-irradiation disintegration rates for each reaction. NAC also compiles a product isotope inventory containing the isotope name, the disintegration rate, the gamma-ray source strength, and the absorbed dose rate at 1 meter from an unshielded point source. The inducedmore » activity is calculated as a function of irradiation and decay times; the effect of cyclic irradiation can also be calculated.« less

  3. An in-depth evaluation of accuracy and precision in Hg isotopic analysis via pneumatic nebulization and cold vapor generation multi-collector ICP-mass spectrometry.

    PubMed

    Rua-Ibarz, Ana; Bolea-Fernandez, Eduardo; Vanhaecke, Frank

    2016-01-01

    Mercury (Hg) isotopic analysis via multi-collector inductively coupled plasma (ICP)-mass spectrometry (MC-ICP-MS) can provide relevant biogeochemical information by revealing sources, pathways, and sinks of this highly toxic metal. In this work, the capabilities and limitations of two different sample introduction systems, based on pneumatic nebulization (PN) and cold vapor generation (CVG), respectively, were evaluated in the context of Hg isotopic analysis via MC-ICP-MS. The effect of (i) instrument settings and acquisition parameters, (ii) concentration of analyte element (Hg), and internal standard (Tl)-used for mass discrimination correction purposes-and (iii) different mass bias correction approaches on the accuracy and precision of Hg isotope ratio results was evaluated. The extent and stability of mass bias were assessed in a long-term study (18 months, n = 250), demonstrating a precision ≤0.006% relative standard deviation (RSD). CVG-MC-ICP-MS showed an approximately 20-fold enhancement in Hg signal intensity compared with PN-MC-ICP-MS. For CVG-MC-ICP-MS, the mass bias induced by instrumental mass discrimination was accurately corrected for by using either external correction in a sample-standard bracketing approach (SSB) or double correction, consisting of the use of Tl as internal standard in a revised version of the Russell law (Baxter approach), followed by SSB. Concomitant matrix elements did not affect CVG-ICP-MS results. Neither with PN, nor with CVG, any evidence for mass-independent discrimination effects in the instrument was observed within the experimental precision obtained. CVG-MC-ICP-MS was finally used for Hg isotopic analysis of reference materials (RMs) of relevant environmental origin. The isotopic composition of Hg in RMs of marine biological origin testified of mass-independent fractionation that affected the odd-numbered Hg isotopes. While older RMs were used for validation purposes, novel Hg isotopic data are provided for the

  4. Application of dual carbon-bromine isotope analysis for investigating abiotic transformations of tribromoneopentyl alcohol (TBNPA).

    PubMed

    Kozell, Anna; Yecheskel, Yinon; Balaban, Noa; Dror, Ishai; Halicz, Ludwik; Ronen, Zeev; Gelman, Faina

    2015-04-01

    Many of polybrominated organic compounds, used as flame retardant additives, belong to the group of persistent organic pollutants. Compound-specific isotope analysis is one of the potential analytical tools for investigating their fate in the environment. However, the isotope effects associated with transformations of brominated organic compounds are still poorly explored. In the present study, we investigated carbon and bromine isotope fractionation during degradation of tribromoneopentyl alcohol (TBNPA), one of the widely used flame retardant additives, in three different chemical processes: transformation in aqueous alkaline solution (pH 8); reductive dehalogenation by zero-valent iron nanoparticles (nZVI) in anoxic conditions; oxidative degradation by H2O2 in the presence of CuO nanoparticles (nCuO). Two-dimensional carbon-bromine isotope plots (δ(13)C/Δ(81)Br) for each reaction gave different process-dependent isotope slopes (Λ(C/Br)): 25.2 ± 2.5 for alkaline hydrolysis (pH 8); 3.8 ± 0.5 for debromination in the presence of nZVI in anoxic conditions; ∞ in the case of catalytic oxidation by H2O2 with nCuO. The obtained isotope effects for both elements were generally in agreement with the values expected for the suggested reaction mechanisms. The results of the present study support further applications of dual carbon-bromine isotope analysis as a tool for identification of reaction pathway during transformations of brominated organic compounds in the environment.

  5. Liquid chromatography/electrospray ionization/isotopic dilution mass spectrometry analysis of n-(phosphonomethyl) glycine and mass spectrometry analysis of aminomethyl phosphonic acid in environmental water and vegetation matrixes.

    PubMed

    Grey, L; Nguyen, B; Yang, P

    2001-01-01

    A liquid chromatography/electrospray/mass spectrometry (LC/ES/MS) method was developed for the analysis of glyphosate (n-phosphonomethyl glycine) and its metabolite, aminomethyl phosphonic acid (AMPA) using isotope-labelled glyphosate as a method surrogate. Optimized parameters were achieved to derivatize glyphosate and AMPA using 9-fluorenylmethyl chloroformate (FMOC-Cl) in borate buffer prior to a reversed-phase LC analysis. Method spike recovery data obtained using laboratory and real world sample matrixes indicated an excellent correlation between the recovery of the native and isotope-labelled glyphosate. Hence, the first performance-based, isotope dilution MS method with superior precision, accuracy, and data quality was developed for the analysis of glyphosate. There was, however, no observable correlation between the isotope-labelled glyphosate and AMPA. Thus, the use of this procedure for the accurate analysis of AMPA was not supported. Method detection limits established using standard U.S. Environmental Protection Agency protocol were 0.06 and 0.30 microg/L, respectively, for glyphosate and AMPA in water matrixes and 0.11 and 0.53 microg/g, respectively, in vegetation matrixes. Problems, solutions, and the method performance data related to the analysis of chlorine-treated drinking water samples are discussed. Applying this method to other environmental matrixes, e.g., soil, with minimum modifications is possible, assuring accurate, multimedia studies of glyphosate concentration in the environment and the delivery of useful multimedia information for regulatory applications.

  6. High information throughput analysis of nucleotides and their isotopically enriched isotopologues by direct-infusion FTICR-MS.

    PubMed

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

    2012-01-01

    Fourier transform-ion cyclotron resonance-mass spectrometry (FTICR-MS) is capable of acquiring unmatched quality of isotopologue data for stable isotope resolved metabolomics (SIRM). This capability drives the need for a continuous ion introduction for obtaining optimal isotope ratios. Here we report the simultaneous analysis of mono and dinucleotides from crude polar extracts by FTICR-MS by adapting an ion-pairing sample preparation method for LC-MS analysis. This involves a rapid cleanup of extracted nucleotides on pipet tips containing a C(18) stationary phase, which enabled global analysis of nucleotides and their (13)C isotopologues at nanomolar concentrations by direct infusion nanoelectrospray FTICR-MS with 5 minutes of data acquisition. The resolution and mass accuracy enabled computer-assisted unambiguous assignment of most nucleotide species, including all phosphorylated forms of the adenine, guanine, uracil and cytosine nucleotides, NAD(+), NADH, NADP(+), NADPH, cyclic nucleotides, several UDP-hexoses, and all their (13)C isotopologues. The method was applied to a SIRM study on human lung adenocarcinoma A549 cells grown in [U-(13)C] glucose with or without the anti-cancer agent methylseleninic acid. At m/z resolving power of 400,000, (13)C-isotopologues of nucleotides were fully resolved from all other elemental isotopologues, thus allowing their (13)C fractional enrichment to be accurately determined. The method achieves both high sample and high information throughput analysis of nucleotides for metabolic pathway reconstruction in SIRM investigations.

  7. Analysis of hydraulic fracturing flowback and produced waters using accurate mass: identification of ethoxylated surfactants.

    PubMed

    Thurman, E Michael; Ferrer, Imma; Blotevogel, Jens; Borch, Thomas

    2014-10-01

    Two series of ethylene oxide (EO) surfactants, polyethylene glycols (PEGs from EO3 to EO33) and linear alkyl ethoxylates (LAEs C-9 to C-15 with EO3-EO28), were identified in hydraulic fracturing flowback and produced water using a new application of the Kendrick mass defect and liquid chromatography/quadrupole-time-of-flight mass spectrometry. The Kendrick mass defect differentiates the proton, ammonium, and sodium adducts in both singly and doubly charged forms. A structural model of adduct formation is presented, and binding constants are calculated, which is based on a spherical cagelike conformation, where the central cation (NH4(+) or Na(+)) is coordinated with ether oxygens. A major purpose of the study was the identification of the ethylene oxide (EO) surfactants and the construction of a database with accurate masses and retention times in order to unravel the mass spectral complexity of surfactant mixtures used in hydraulic fracturing fluids. For example, over 500 accurate mass assignments are made in a few seconds of computer time, which then is used as a fingerprint chromatogram of the water samples. This technique is applied to a series of flowback and produced water samples to illustrate the usefulness of ethoxylate "fingerprinting", in a first application to monitor water quality that results from fluids used in hydraulic fracturing. PMID:25164376

  8. Time-Accurate Simulations and Acoustic Analysis of Slat Free-Shear-Layer. Part 2

    NASA Technical Reports Server (NTRS)

    Khorrami, Mehdi R.; Singer, Bart A.; Lockard, David P.

    2002-01-01

    Unsteady computational simulations of a multi-element, high-lift configuration are performed. Emphasis is placed on accurate spatiotemporal resolution of the free shear layer in the slat-cove region. The excessive dissipative effects of the turbulence model, so prevalent in previous simulations, are circumvented by switching off the turbulence-production term in the slat cove region. The justifications and physical arguments for taking such a step are explained in detail. The removal of this excess damping allows the shear layer to amplify large-scale structures, to achieve a proper non-linear saturation state, and to permit vortex merging. The large-scale disturbances are self-excited, and unlike our prior fully turbulent simulations, no external forcing of the shear layer is required. To obtain the farfield acoustics, the Ffowcs Williams and Hawkings equation is evaluated numerically using the simulated time-accurate flow data. The present comparison between the computed and measured farfield acoustic spectra shows much better agreement for the amplitude and frequency content than past calculations. The effect of the angle-of-attack on the slat's flow features radiated acoustic field are also simulated presented.

  9. Compound-specific isotope analysis of diesel fuels in a forensic investigation

    PubMed Central

    Muhammad, Syahidah A.; Frew, Russell D.; Hayman, Alan R.

    2015-01-01

    Compound-specific isotope analysis (CSIA) offers great potential as a tool to provide chemical evidence in a forensic investigation. Many attempts to trace environmental oil spills were successful where isotopic values were particularly distinct. However, difficulties arise when a large data set is analyzed and the isotopic differences between samples are subtle. In the present study, discrimination of diesel oils involved in a diesel theft case was carried out to infer the relatedness of the samples to potential source samples. This discriminatory analysis used a suite of hydrocarbon diagnostic indices, alkanes, to generate carbon and hydrogen isotopic data of the compositions of the compounds which were then processed using multivariate statistical analyses to infer the relatedness of the data set. The results from this analysis were put into context by comparing the data with the δ13C and δ2H of alkanes in commercial diesel samples obtained from various locations in the South Island of New Zealand. Based on the isotopic character of the alkanes, it is suggested that diesel fuels involved in the diesel theft case were distinguishable. This manuscript shows that CSIA when used in tandem with multivariate statistical analysis provide a defensible means to differentiate and source-apportion qualitatively similar oils at the molecular level. This approach was able to overcome confounding challenges posed by the near single-point source of origin, i.e., the very subtle differences in isotopic values between the samples. PMID:25774366

  10. Compound-Specific Isotope Analysis of Diesel Fuels in a Forensic Investigation

    NASA Astrophysics Data System (ADS)

    Muhammad, Syahidah; Frew, Russell; Hayman, Alan

    2015-02-01

    Compound-specific isotope analysis (CSIA) offers great potential as a tool to provide chemical evidence in a forensic investigation. Many attempts to trace environmental oil spills were successful where isotopic values were particularly distinct. However, difficulties arise when a large data set is analyzed and the isotopic differences between samples are subtle. In the present study, discrimination of diesel oils involved in a diesel theft case was carried out to infer the relatedness of the samples to potential source samples. This discriminatory analysis used a suite of hydrocarbon diagnostic indices, alkanes, to generate carbon and hydrogen isotopic data of the compositions of the compounds which were then processed using multivariate statistical analyses to infer the relatedness of the data set. The results from this analysis were put into context by comparing the data with the δ13C and δ2H of alkanes in commercial diesel samples obtained from various locations in the South Island of New Zealand. Based on the isotopic character of the alkanes, it is suggested that diesel fuels involved in the diesel theft case were distinguishable. This manuscript shows that CSIA when used in tandem with multivariate statistical analysis provide a defensible means to differentiate and source-apportion qualitatively similar oils at the molecular level. This approach was able to overcome confounding challenges posed by the near single-point source of origin i.e. the very subtle differences in isotopic values between the samples.

  11. Determination of plutonium-239, thorium-232, and natural uranium isotopic concentrations in biological samples using photofission track analysis

    NASA Astrophysics Data System (ADS)

    Parry, James Roswell

    Fission track analysis (FTA) has many uses in the scientific community including but not limited to geological dating, neutron flux mapping, and dose reconstruction. The common method of fission for FTA is through neutrons from a nuclear reactor. This dissertation investigates the use of bremsstrahlung radiation produced from an electron linear accelerator to induce fission in FTA samples. This provides a means of simultaneously measuring the amount of Pu-239, U-nat, and Th-232 in a single sample. The benefit of measuring the three isotopes simultaneously is the possible elimination of costly and time consuming chemical processing for dose reconstruction samples. Samples containing the three isotopes were irradiated in two different bremsstrahlung spectra and a neutron spectrum to determine the amount of Pu-239, U-nat, and Th-232 in the samples. The reaction rate from the calibration samples and the counted fission tracks on the samples were used in determining the concentration of each isotope in the samples. The results were accurate to within a factor of two or three, showing that the method can work to predict the concentrations of multiple isotopes in a sample. The limitations of current accelerators and detectors limits the application of this specific procedure to higher concentrations of isotopes. The method detection limits for Pu-239, U-nat, and Th-232 are 20 pCi, 1 fCi, and 0.4 flCI respectively. Analysis of extremely low concentrations of isotopes would require the use of different detectors such as quartz due to the embrittlement encountered in the Lexan at high exposures. Cracking of the Texan detectors started to appear at a fluence of about 2 x 1018 electrons from the accelerator. This may be partly due to the beam stop not being an adequate thickness. The procedure is likely limited to specialty applications for the near term. However, with the world concerns of exposure to depleted uranium, this procedure may find applications in this area since

  12. Femtosecond Laser Ablation Multicollector ICPMS Analysis of Uranium Isotopes in NIST Glass

    SciTech Connect

    Duffin, Andrew M.; Springer, Kellen WE; Ward, Jesse D.; Jarman, Kenneth D.; Robinson, John W.; Endres, Mackenzie C.; Hart, Garret L.; Gonzalez, Jhanis J.; Oropeza, Dayana; Russo, Richard; Willingham, David G.; Naes, Benjamin E.; Fahey, Albert J.; Eiden, Gregory C.

    2015-02-06

    We have utilized femtosecond laser ablation coupled to multi-collector inductively couple plasma mass spectrometry to measure the uranium isotopic content of NIST 61x (x=0,2,4,6) glasses. The uranium content of these glasses is a linear two-component mixing between isotopically natural uranium and the isotopically depleted spike used in preparing the glasses. Laser ablation results match extremely well, generally within a few ppm, with solution analysis following sample dissolution and chemical separation. In addition to isotopic data, sample utilization efficiency measurements indicate that over 1% of ablated uranium atoms reach a mass spectrometer detector, making this technique extremely efficient. Laser sampling also allows for spatial analysis and our data indicate that rare uranium concentration inhomogeneities exist in NIST 616 glass.

  13. Optimizing Analysis of Stable Isotope Breath Tests to Estimate Gastric Emptying of Solids

    PubMed Central

    Odunsi, Suwebatu T.; Camilleri, Michael; Szarka, Lawrence A.; Zinsmeister, Alan R.

    2009-01-01

    Breath tests using 13C-substrates have been proposed for the measurement of gastric emptying (GE). The mathematical analysis of the breath 13CO2 excretion that most accurately predicts GE t1/2 from simultaneous scintigraphy is unresolved. Aim To compare 5 mathematical methods to estimate GE t½ by breath test (BT) with t½ from simultaneous scintigraphy. Methods Data acquired from a dual-labeled solid-liquid meal containing 99mTc sulfur colloid and 13C-Spirulina platensis from 57 healthy volunteers were used to compare 4 mathematical methods reported in the literature (Ghoos method; generalized linear regression [Viramontes]; linear regression [Szarka]; Wagner-Nelson method) and the total cumulative breath 13CO2 excretion with ≥ 12 breath samples collected over at least 4 hours. The concordance correlation coefficient (CCC) for the t½ results obtained with each method using breath test data was compared with the results obtained with scintigraphy. Results The linear regression and generalized linear regression methods used 5 samples at 45, 90, 120, 150 and 180 minutes. All methods, except for the Wagner-Nelson method, resulted in mean GE t½ that approximated t½ obtained with scintigraphy. The highest CCC was observed with the linear regression method. Simple cumulative excretion of breath 13CO2 provides a better CCC than the Ghoos method. Conclusion The linear regression and generalized linear regression methods (which also require relatively few breath samples) provide the most accurate analyses of breath 13CO2 excretion in stable isotope GEBT. PMID:19309440

  14. Quantifying plant phenotypes with isotopic labeling and metabolic flux analysis

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Analyses of metabolic flux using stable isotopes in plants have traditionally been restricted to tissues with presumed homogeneous cell populations such as developing seeds, cell suspensions, or cultured roots and root tips. It is now possible to describe these and other more complex tissues such a...

  15. STABLE CHLORINE ISOTOPE ANALYSIS OF CHLORINATED ORGANIC CONTAMINANTS

    EPA Science Inventory

    The biogeochemical cycling of chlorinated organic contaminants in the environment is often difficult to understand because of the complex distributions of these compounds and variability of sources. To address these issues from an isotopic perspective, we have measured the, 37Cl...

  16. Performance testing of the upgraded uranium isotopics multi-group analysis code MGAU

    NASA Astrophysics Data System (ADS)

    Berlizov, A. N.; Gunnink, R.; Zsigrai, J.; Nguyen, C. T.; Tryshyn, V. V.

    2007-06-01

    The paper describes recent developments of the MGAU (Multi-Group Analysis for Uranium) method, which resulted in the creation of an upgraded version 4.0 of the MGAU code. The major improvements concerned the procedure of the intrinsic efficiency calibration, particularly in the 120-205 keV region. The results of the tests carried out with the use of certified reference uranium isotopic materials SRM 969 and CRM 146 showed a significantly improved performance of the upgraded MGAU code for the accurate characterization of 235U and 234U abundances. The relative systematic biases of the abundances measured were evaluated not to exceed 1% and 3% over the concentration intervals 0.32-93.2 and 0.002-0.98 mass% for 235U and 234U, respectively. The influence of an up to 4-5 mm steel equivalent absorber and sample thickness on the measurement results was found to be much smaller than in previous versions of the code.

  17. Improved approach for analyzing bromophenols in seafood using stable isotope dilution analysis in combination with SPME.

    PubMed

    Fuller, Steve C; Frank, Damian C; Fitzhenry, Matthew J; Smyth, Heather E; Poole, Sue E

    2008-09-24

    An analytical method for the measurement of five naturally occurring bromophenols of sensory relevance in seafood (barramundi and prawns) is presented. The method combines simultaneous distillation-extraction followed by alkaline back extraction of a hexane extract and subsequent acetylation of the bromophenols. Analysis of the bromophenol acetates was accomplished by headspace solid phase microextraction and gas chromatography-mass spectrometry using selected ion monitoring. The addition of (13)C 6 bromophenol stable isotope internal standards for each of the five congeners studied permitted the accurate quantitation of 2-bromophenol, 4-bromophenol, 2,6-dibromophenol, 2,4-dibromophenol, and 2,4,6-tribromophenol down to a limit of quantification of 0.05 ng/g of fish flesh. The method indicated acceptable precision and repeatability and excellent linearity over the typical concentration range of these compounds in seafood (0.5-50 ng/g). The analytical method was applied to determine the concentration of bromophenols in a range of farmed and wild barramundi and prawns and was also used to monitor bromophenol uptake in a pilot feeding trial. PMID:18754626

  18. Analysis of acrylamide in coffee and cocoa by isotope dilution liquid chromatography-tandem mass spectrometry.

    PubMed

    Aguas, Patricia C; Fitzhenry, Matthew J; Giannikopoulos, Georgina; Varelis, Peter

    2006-08-01

    An accurate and precise method for the quantification of acrylamide using stable isotope dilution liquid chromatography-tandem mass spectrometry was developed and used to measure acrylamide in coffee and cocoa samples. The sample preparation involved extraction of the analyte and its internal standard, 13C3-acrylamide, into water and subsequent defatting of the aqueous extract with dichloromethane. An aliquot of the resulting aqueous extract was then azeotropically dried under reduced pressure and subsequently purified using an aminopropyl-bonded silica cartridge. The purified extracts were then chromatographed on a 5-microm 2.1 x 150 mm Hypercarb column, the effluent of which was monitored for the analyte and its internal standard using positive-ion APCI-selected reaction monitoring. The intra-laboratory reproducibility of the method, expressed as a relative coefficient of variation (%, n=5), was determined at four levels of concentration (12.3, 42.3, 139.3 and 464.8 microg kg(-1)) and was found to vary between 0.6-2.5%. The accuracy of the method was assessed using a reference sample of coffee. The average result obtained using our method differed from the assigned value of the reference material by less than 1%. An analysis of a cocoa sample revealed that the method is capable of precisely estimating acrylamide in challenging matrices down to a level of at least 12.3 microg kg(-1). PMID:16819634

  19. Mass spectrometric analysis of isotope effects in bioconversion of benzene to cyclohexanone

    NASA Astrophysics Data System (ADS)

    Nam, In-Hyun; Murugesan, Kumarasamy; Kim, Young-Mo; Yang, In-Hee; Chang, Yoon-Seok

    2006-06-01

    Pseudomonas veronii strain PH-03 has been shown to convert benzene to cyclohexanone through phenol. Mass spectrometry results revealed that unusual isotopic effects have been occurred in the transformation product, cyclohexanone. The isotopic composition was strongly depends on the compound specific hydrogen or oxygen source. The exchange of labile deuterium atoms has been investigated through electrospray ionization liquid chromatography mass spectrometry. The mass spectrometric analysis of biotransformation products enabled the proposal of a corresponding bioconversion pathway.

  20. Application of double-spike isotope dilution for the accurate determination of Cr(III), Cr(VI) and total Cr in yeast.

    PubMed

    Yang, Lu; Ciceri, Elena; Mester, Zoltán; Sturgeon, Ralph E

    2006-11-01

    A method is presented for the simultaneous determination of Cr(III) and Cr(VI) in yeast using species-specific double-spike isotope dilution (SSDSID) with anion-exchange liquid chromatography (LC) separation and sector field inductively coupled plasma mass spectrometric (SF-ICP-MS) detection. Total Cr is quantitated using ID SF-ICP-MS. Samples were digested on a hot plate at 95+/-2 degrees C for 6 h in an alkaline solution of 0.5 M NaOH and 0.28 M Na2CO3 for the determination of Cr(III) and Cr(VI), whereas microwave-assisted decomposition with HNO3 and H2O2 was used for the determination of total Cr. Concentrations of 2,014+/-16, 1,952+/-103 and 76+/-48 mg kg-1 (one standard deviation, n=4, 3, 3), respectively were obtained for total Cr, Cr(III) and Cr(VI) in the yeast sample. Significant oxidation of Cr(III) to Cr(VI) (24.2+/-7.6% Cr(III) oxidized, n=3) and reduction of Cr(VI) to Cr(III) (37.6+/-6.5% Cr(VI) reduced, n=3) occurred during alkaline extraction and subsequent chromatographic separation at pH 7. Despite this significant bidirectional redox transformation, quantitative recoveries for both Cr(III) and Cr(VI) were achieved using the SSDSID method. In addition, mass balance between total Cr and the sum of Cr(III) and Cr(VI) concentrations was achieved. Method detection limits of 0.3, 2 and 30 mg kg-1 were obtained for total Cr, Cr(VI) and Cr(III), respectively, based on a 0.2-g sub-sample.

  1. The ALHAMBRA survey: accurate merger fractions derived by PDF analysis of photometrically close pairs

    NASA Astrophysics Data System (ADS)

    López-Sanjuan, C.; Cenarro, A. J.; Varela, J.; Viironen, K.; Molino, A.; Benítez, N.; Arnalte-Mur, P.; Ascaso, B.; Díaz-García, L. A.; Fernández-Soto, A.; Jiménez-Teja, Y.; Márquez, I.; Masegosa, J.; Moles, M.; Pović, M.; Aguerri, J. A. L.; Alfaro, E.; Aparicio-Villegas, T.; Broadhurst, T.; Cabrera-Caño, J.; Castander, F. J.; Cepa, J.; Cerviño, M.; Cristóbal-Hornillos, D.; Del Olmo, A.; González Delgado, R. M.; Husillos, C.; Infante, L.; Martínez, V. J.; Perea, J.; Prada, F.; Quintana, J. M.

    2015-04-01

    Aims: Our goal is to develop and test a novel methodology to compute accurate close-pair fractions with photometric redshifts. Methods: We improved the currently used methodologies to estimate the merger fraction fm from photometric redshifts by (i) using the full probability distribution functions (PDFs) of the sources in redshift space; (ii) including the variation in the luminosity of the sources with z in both the sample selection and the luminosity ratio constrain; and (iii) splitting individual PDFs into red and blue spectral templates to reliably work with colour selections. We tested the performance of our new methodology with the PDFs provided by the ALHAMBRA photometric survey. Results: The merger fractions and rates from the ALHAMBRA survey agree excellently well with those from spectroscopic work for both the general population and red and blue galaxies. With the merger rate of bright (MB ≤ -20-1.1z) galaxies evolving as (1 + z)n, the power-law index n is higher for blue galaxies (n = 2.7 ± 0.5) than for red galaxies (n = 1.3 ± 0.4), confirming previous results. Integrating the merger rate over cosmic time, we find that the average number of mergers per galaxy since z = 1 is Nmred = 0.57 ± 0.05 for red galaxies and Nmblue = 0.26 ± 0.02 for blue galaxies. Conclusions: Our new methodology statistically exploits all the available information provided by photometric redshift codes and yields accurate measurements of the merger fraction by close pairs from using photometric redshifts alone. Current and future photometric surveys will benefit from this new methodology. Based on observations collected at the German-Spanish Astronomical Center, Calar Alto, jointly operated by the Max-Planck-Institut für Astronomie (MPIA) at Heidelberg and the Instituto de Astrofísica de Andalucía (CSIC).The catalogues, probabilities, and figures of the ALHAMBRA close pairs detected in Sect. 5.1 are available at http://https://cloud.iaa.csic.es/alhambra/catalogues/ClosePairs

  2. Quantifying plant phenotypes with isotopic labeling & metabolic flux analysis.

    PubMed

    Allen, Doug K

    2016-02-01

    Analyses of metabolic flux using stable isotopes in plants have traditionally been restricted to tissues with presumed homogeneous cell populations and long metabolic steady states such as developing seeds, cell suspensions, or cultured roots and root tips. It is now possible to describe these and other metabolically more dynamic tissues such as leaves in greater detail using novel methods in mass spectrometry, isotope labeling strategies, and transient labeling-based flux analyses. Such studies are necessary for a systems level description of plant function that more closely represents biological reality, and provides insights into the genes that will need to be modified as natural resources become ever more limited and environments change. PMID:26613198

  3. The conflict between cheetahs and humans on Namibian farmland elucidated by stable isotope diet analysis.

    PubMed

    Voigt, Christian C; Thalwitzer, Susanne; Melzheimer, Jörg; Blanc, Anne-Sophie; Jago, Mark; Wachter, Bettina

    2014-01-01

    Large areas of Namibia are covered by farmland, which is also used by game and predator species. Because it can cause conflicts with farmers when predators, such as cheetahs (Acinonyx jubatus), hunt livestock, we assessed whether livestock constitutes a significant part of the cheetah diet by analysing the stable isotope composition of blood and tissue samples of cheetahs and their potential prey species. According to isotopic similarities, we defined three isotopic categories of potential prey: members of a C4 food web with high δ15N values (gemsbok, cattle, springhare and guinea fowl) and those with low δ15N values (hartebeest, warthog), and members of a C3 food web, namely browsers (eland, kudu, springbok, steenbok and scrub hare). We quantified the trophic discrimination of heavy isotopes in cheetah muscle in 9 captive individuals and measured an enrichment for 15N (3.2‰) but not for 13C in relation to food. We captured 53 free-ranging cheetahs of which 23 were members of groups. Cheetahs of the same group were isotopically distinct from members of other groups, indicating that group members shared their prey. Solitary males (n = 21) and males in a bachelor groups (n = 11) fed mostly on hartebeest and warthogs, followed by browsers in case of solitary males, and by grazers with high δ15N values in case of bachelor groups. Female cheetahs (n = 9) predominantly fed on browsers and used also hartebeest and warthogs. Mixing models suggested that the isotopic prey category that included cattle was only important, if at all, for males living in bachelor groups. Stable isotope analysis of fur, muscle, red blood cells and blood plasma in 9 free-ranging cheetahs identified most individuals as isotopic specialists, focussing on isotopically distinct prey categories as their food. PMID:25162403

  4. Carbon and chlorine isotope analysis to identify abiotic degradation pathways of 1,1,1-trichloroethane.

    PubMed

    Palau, Jordi; Shouakar-Stash, Orfan; Hunkeler, Daniel

    2014-12-16

    This study investigates dual C-Cl isotope fractionation during 1,1,1-TCA transformation by heat-activated persulfate (PS), hydrolysis/dehydrohalogenation (HY/DH) and Fe(0). Compound-specific chlorine isotope analysis of 1,1,1-TCA was performed for the first time, and transformation-associated isotope fractionation ε bulk C and ε bulk Cl values were -4.0 ± 0.2‰ and no chlorine isotope fractionation with PS, -1.6 ± 0.2‰ and -4.7 ± 0.1‰ for HY/DH, -7.8 ± 0.4‰ and -5.2 ± 0.2‰ with Fe(0). Distinctly different dual isotope slopes (Δδ13C/Δδ37Cl): ∞ with PS, 0.33 ± 0.04 for HY/DH and 1.5 ± 0.1 with Fe(0) highlight the potential of this approach to identify abiotic degradation pathways of 1,1,1-TCA in the field. The trend observed with PS agreed with a C-H bond oxidation mechanism in the first reaction step. For HY/DH and Fe(0) pathways, different slopes were obtained although both pathways involve cleavage of a C-Cl bond in their initial reaction step. In contrast to the expected larger primary carbon isotope effects relative to chlorine for C-Cl bond cleavage, ε bulk C < ε bulk Cl was observed for HY/DH and in a similar range for reduction by Fe(0), suggesting the contribution of secondary chlorine isotope effects. Therefore, different magnitude of secondary chlorine isotope effects could at least be partly responsible for the distinct slopes between HY/DH and Fe(0) pathways. Following this dual isotope approach, abiotic transformation processes can unambiguously be identified and quantified.

  5. Degradation and Volatilization of Chlorofluorocarbons in Contaminated Groundwater Explored by Stable Carbon Isotope Analysis

    NASA Astrophysics Data System (ADS)

    Horst, A.; Lacrampe-Couloume, G.; Sherwood Lollar, B.

    2015-12-01

    Chlorofluorocarbons (CFCs) are ozone depleting compounds whose production was phased out by the regulations of the Montreal Protocol (1987). Accidental release and disposal also led to contamination of groundwater at many locations, however, and this legacy persists. Although very stable, CFCs may degrade via abiotic and biotic pathways. Quantification of the degree of transformation of CFCs has been challenging due to other processes such as dilution, sorption and volatilization. Compound specific stable carbon isotope analysis (CSIA) has been successfully applied for a variety of priority pollutants to distinguish degradation from other processes and to quantify transformation rates. A Purge & Trap - CSIA method developed in our lab was applied to determine the stable carbon isotopic signature of CFCs and HCFCs (hydrochlorofluorocarbons) in groundwater samples from a contaminated site. Preliminary results suggest that degradation of CFCs and HCFCs may result in enriched δ13C values, consistent with fractionation during bond breakage as has been reported for many other hydrocarbon pollutants. The effect of volatile loss during sampling on the isotopic signatures of CFCs was examined in laboratory experiments. Volatilization from pure phase CFCs showed a small inverse isotope effect during open system volatilization, opposite to the normal isotope effect generally observed during biodegradation. For volatilization of CFCs dissolved in water a much smaller isotope effect was observed. An important result from this work is that any volatile loss may introduce only a small change in CFC isotopic signatures in groundwater, and importantly, due to the opposite direction of isotope effects associated with volatilization versus degradation, any effects of volatile loss on the isotopic signatures cannot be confused with transformation of CFCs. At most, volatilization might contribute to a conservative estimate of the extent of degradation.

  6. Degradation and Volatilization of Chlorofluorocarbons in Contaminated Groundwater Explored by Stable Carbon Isotope Analysis

    NASA Astrophysics Data System (ADS)

    Hangx, S.; Pijnenburg, R. P.; Niemeijer, A. R.; Bakker, E.; Samuelson, J. E.; Spiers, C. J.

    2014-12-01

    Chlorofluorocarbons (CFCs) are ozone depleting compounds whose production was phased out by the regulations of the Montreal Protocol (1987). Accidental release and disposal also led to contamination of groundwater at many locations, however, and this legacy persists. Although very stable, CFCs may degrade via abiotic and biotic pathways. Quantification of the degree of transformation of CFCs has been challenging due to other processes such as dilution, sorption and volatilization. Compound specific stable carbon isotope analysis (CSIA) has been successfully applied for a variety of priority pollutants to distinguish degradation from other processes and to quantify transformation rates. A Purge & Trap - CSIA method developed in our lab was applied to determine the stable carbon isotopic signature of CFCs and HCFCs (hydrochlorofluorocarbons) in groundwater samples from a contaminated site. Preliminary results suggest that degradation of CFCs and HCFCs may result in enriched δ13C values, consistent with fractionation during bond breakage as has been reported for many other hydrocarbon pollutants. The effect of volatile loss during sampling on the isotopic signatures of CFCs was examined in laboratory experiments. Volatilization from pure phase CFCs showed a small inverse isotope effect during open system volatilization, opposite to the normal isotope effect generally observed during biodegradation. For volatilization of CFCs dissolved in water a much smaller isotope effect was observed. An important result from this work is that any volatile loss may introduce only a small change in CFC isotopic signatures in groundwater, and importantly, due to the opposite direction of isotope effects associated with volatilization versus degradation, any effects of volatile loss on the isotopic signatures cannot be confused with transformation of CFCs. At most, volatilization might contribute to a conservative estimate of the extent of degradation.

  7. The conflict between cheetahs and humans on Namibian farmland elucidated by stable isotope diet analysis.

    PubMed

    Voigt, Christian C; Thalwitzer, Susanne; Melzheimer, Jörg; Blanc, Anne-Sophie; Jago, Mark; Wachter, Bettina

    2014-01-01

    Large areas of Namibia are covered by farmland, which is also used by game and predator species. Because it can cause conflicts with farmers when predators, such as cheetahs (Acinonyx jubatus), hunt livestock, we assessed whether livestock constitutes a significant part of the cheetah diet by analysing the stable isotope composition of blood and tissue samples of cheetahs and their potential prey species. According to isotopic similarities, we defined three isotopic categories of potential prey: members of a C4 food web with high δ15N values (gemsbok, cattle, springhare and guinea fowl) and those with low δ15N values (hartebeest, warthog), and members of a C3 food web, namely browsers (eland, kudu, springbok, steenbok and scrub hare). We quantified the trophic discrimination of heavy isotopes in cheetah muscle in 9 captive individuals and measured an enrichment for 15N (3.2‰) but not for 13C in relation to food. We captured 53 free-ranging cheetahs of which 23 were members of groups. Cheetahs of the same group were isotopically distinct from members of other groups, indicating that group members shared their prey. Solitary males (n = 21) and males in a bachelor groups (n = 11) fed mostly on hartebeest and warthogs, followed by browsers in case of solitary males, and by grazers with high δ15N values in case of bachelor groups. Female cheetahs (n = 9) predominantly fed on browsers and used also hartebeest and warthogs. Mixing models suggested that the isotopic prey category that included cattle was only important, if at all, for males living in bachelor groups. Stable isotope analysis of fur, muscle, red blood cells and blood plasma in 9 free-ranging cheetahs identified most individuals as isotopic specialists, focussing on isotopically distinct prey categories as their food.

  8. The Conflict between Cheetahs and Humans on Namibian Farmland Elucidated by Stable Isotope Diet Analysis

    PubMed Central

    Voigt, Christian C.; Thalwitzer, Susanne; Melzheimer, Jörg; Blanc, Anne-Sophie; Jago, Mark; Wachter, Bettina

    2014-01-01

    Large areas of Namibia are covered by farmland, which is also used by game and predator species. Because it can cause conflicts with farmers when predators, such as cheetahs (Acinonyx jubatus), hunt livestock, we assessed whether livestock constitutes a significant part of the cheetah diet by analysing the stable isotope composition of blood and tissue samples of cheetahs and their potential prey species. According to isotopic similarities, we defined three isotopic categories of potential prey: members of a C4 food web with high δ15N values (gemsbok, cattle, springhare and guinea fowl) and those with low δ15N values (hartebeest, warthog), and members of a C3 food web, namely browsers (eland, kudu, springbok, steenbok and scrub hare). We quantified the trophic discrimination of heavy isotopes in cheetah muscle in 9 captive individuals and measured an enrichment for 15N (3.2‰) but not for 13C in relation to food. We captured 53 free-ranging cheetahs of which 23 were members of groups. Cheetahs of the same group were isotopically distinct from members of other groups, indicating that group members shared their prey. Solitary males (n = 21) and males in a bachelor groups (n = 11) fed mostly on hartebeest and warthogs, followed by browsers in case of solitary males, and by grazers with high δ15N values in case of bachelor groups. Female cheetahs (n = 9) predominantly fed on browsers and used also hartebeest and warthogs. Mixing models suggested that the isotopic prey category that included cattle was only important, if at all, for males living in bachelor groups. Stable isotope analysis of fur, muscle, red blood cells and blood plasma in 9 free-ranging cheetahs identified most individuals as isotopic specialists, focussing on isotopically distinct prey categories as their food. PMID:25162403

  9. Assessing connectivity of estuarine fishes based on stable isotope ratio analysis

    NASA Astrophysics Data System (ADS)

    Herzka, Sharon Z.

    2005-07-01

    Assessing connectivity is fundamental to understanding the population dynamics of fishes. I propose that isotopic analyses can greatly contribute to studies of connectivity in estuarine fishes due to the high diversity of isotopic signatures found among estuarine habitats and the fact that variations in isotopic composition at the base of a food web are reflected in the tissues of consumers. Isotopic analysis can be used for identifying nursery habitats and estimating their contribution to adult populations. If movement to a new habitat is accompanied by a shift to foods of distinct isotopic composition, recent immigrants and residents can be distinguished based on their isotopic ratios. Movement patterns thus can be reconstructed based on information obtained from individuals. A key consideration is the rate of isotopic turnover, which determines the length of time that an immigrant to a given habitat will be distinguishable from a longtime resident. A literature survey indicated that few studies have measured turnover rates in fishes and that these have focused on larvae and juveniles. These studies reveal that biomass gain is the primary process driving turnover rates, while metabolic turnover is either minimal or undetectable. Using a simple dilution model and biomass-specific growth rates, I estimated that young fishes with fast growth rates will reflect the isotopic composition of a new diet within days or weeks. Older or slower-growing individuals may take years or never fully equilibrate. Future studies should evaluate the factors that influence turnover rates in fishes during various stages of the life cycle and in different tissues, as well as explore the potential for combining stable isotope and otolith microstructure analyses to examine the relationship between demographic parameters, movement and connectivity.

  10. TIARA: a database for accurate analysis of multiple personal genomes based on cross-technology

    PubMed Central

    Hong, Dongwan; Park, Sung-Soo; Ju, Young Seok; Kim, Sheehyun; Shin, Jong-Yeon; Kim, Sujung; Yu, Saet-Byeol; Lee, Won-Chul; Lee, Seungbok; Park, Hansoo; Kim, Jong-Il; Seo, Jeong-Sun

    2011-01-01

    High-throughput genomic technologies have been used to explore personal human genomes for the past few years. Although the integration of technologies is important for high-accuracy detection of personal genomic variations, no databases have been prepared to systematically archive genomes and to facilitate the comparison of personal genomic data sets prepared using a variety of experimental platforms. We describe here the Total Integrated Archive of Short-Read and Array (TIARA; http://tiara.gmi.ac.kr) database, which contains personal genomic information obtained from next generation sequencing (NGS) techniques and ultra-high-resolution comparative genomic hybridization (CGH) arrays. This database improves the accuracy of detecting personal genomic variations, such as SNPs, short indels and structural variants (SVs). At present, 36 individual genomes have been archived and may be displayed in the database. TIARA supports a user-friendly genome browser, which retrieves read-depths (RDs) and log2 ratios from NGS and CGH arrays, respectively. In addition, this database provides information on all genomic variants and the raw data, including short reads and feature-level CGH data, through anonymous file transfer protocol. More personal genomes will be archived as more individuals are analyzed by NGS or CGH array. TIARA provides a new approach to the accurate interpretation of personal genomes for genome research. PMID:21051338

  11. Guided resonances on lithium niobate for extremely small electric field detection investigated by accurate sensitivity analysis.

    PubMed

    Qiu, Wentao; Ndao, Abdoulaye; Lu, Huihui; Bernal, Maria-Pilar; Baida, Fadi Issam

    2016-09-01

    We present a theoretical study of guided resonances (GR) on a thin film lithium niobate rectangular lattice photonic crystal by band diagram calculations and 3D Finite Difference Time Domain (FDTD) transmission investigations which cover a broad range of parameters. A photonic crystal with an active zone as small as 13μm×13μm×0.7μm can be easily designed to obtain a resonance Q value in the order of 1000. These resonances are then employed in electric field (E-field) sensing applications exploiting the electro optic (EO) effect of lithium niobate. A local field factor that is calculated locally for each FDTD cell is proposed to accurately estimate the sensitivity of GR based E-field sensor. The local field factor allows well agreement between simulations and reported experimental data therefore providing a valuable method in optimizing the GR structure to obtain high sensitivities. When these resonances are associated with sub-picometer optical spectrum analyzer and high field enhancement antenna design, an E-field probe with a sensitivity of 50 μV/m could be achieved. The results of our simulations could be also exploited in other EO based applications such as EEG (Electroencephalography) or ECG (Electrocardiography) probe and E-field frequency detector with an 'invisible' probe to the field being detected etc. PMID:27607627

  12. An integrative variant analysis pipeline for accurate genotype/haplotype inference in population NGS data

    PubMed Central

    Wang, Yi; Lu, James; Yu, Jin; Gibbs, Richard A.; Yu, Fuli

    2013-01-01

    Next-generation sequencing is a powerful approach for discovering genetic variation. Sensitive variant calling and haplotype inference from population sequencing data remain challenging. We describe methods for high-quality discovery, genotyping, and phasing of SNPs for low-coverage (approximately 5×) sequencing of populations, implemented in a pipeline called SNPTools. Our pipeline contains several innovations that specifically address challenges caused by low-coverage population sequencing: (1) effective base depth (EBD), a nonparametric statistic that enables more accurate statistical modeling of sequencing data; (2) variance ratio scoring, a variance-based statistic that discovers polymorphic loci with high sensitivity and specificity; and (3) BAM-specific binomial mixture modeling (BBMM), a clustering algorithm that generates robust genotype likelihoods from heterogeneous sequencing data. Last, we develop an imputation engine that refines raw genotype likelihoods to produce high-quality phased genotypes/haplotypes. Designed for large population studies, SNPTools' input/output (I/O) and storage aware design leads to improved computing performance on large sequencing data sets. We apply SNPTools to the International 1000 Genomes Project (1000G) Phase 1 low-coverage data set and obtain genotyping accuracy comparable to that of SNP microarray. PMID:23296920

  13. Accurate reliability analysis method for quantum-dot cellular automata circuits

    NASA Astrophysics Data System (ADS)

    Cui, Huanqing; Cai, Li; Wang, Sen; Liu, Xiaoqiang; Yang, Xiaokuo

    2015-10-01

    Probabilistic transfer matrix (PTM) is a widely used model in the reliability research of circuits. However, PTM model cannot reflect the impact of input signals on reliability, so it does not completely conform to the mechanism of the novel field-coupled nanoelectronic device which is called quantum-dot cellular automata (QCA). It is difficult to get accurate results when PTM model is used to analyze the reliability of QCA circuits. To solve this problem, we present the fault tree models of QCA fundamental devices according to different input signals. After that, the binary decision diagram (BDD) is used to quantitatively investigate the reliability of two QCA XOR gates depending on the presented models. By employing the fault tree models, the impact of input signals on reliability can be identified clearly and the crucial components of a circuit can be found out precisely based on the importance values (IVs) of components. So this method is contributive to the construction of reliable QCA circuits.

  14. Mechanical Analysis and Hierarchies of Multi-digit Synergies during Accurate Object Rotation

    PubMed Central

    Zhang, Wei; Olafsdottir, Halla B.; Zatsiorsky, Vladimir M.; Latash, Mark L.

    2009-01-01

    We studied the mechanical variables (the grip force and the total moment of force) and multi-digit synergies at two levels (the virtual finger-thumb level, VF-TH, and the individual finger level, IMRL) of a hypothetical control hierarchy during accurate rotation of a hand-held instrumented handle. Synergies were defined as co-varied changes in elemental variables (forces and moments of force) that stabilize the output at a particular level. Indices of multi-digit synergies showed higher values at the hierarchically higher level (VF-TH) for both normal and tangential forces. The moment of force was stabilized at both hierarchical levels during the steady-state phases but not during the movement. The results support the principles of superposition and of mechanical advantage. They also support an earlier hypothesis on an inherent trade-off between synergies at the two hierarchical levels, although the controller showed more subtle and versatile synergic control than the one hypothesized earlier. PMID:19799165

  15. Compound-Specific Isotope Analysis of Amino Acids for Stardust-Returned Samples

    NASA Technical Reports Server (NTRS)

    Cook, Jamie; Elsila, Jamie E.; Stern J. C.; Glavin, D. P.; Dworkin, J. P.

    2008-01-01

    Significant portions of the early Earth's prebiotic organic inventory , including amino acids, could have been delivered to the Earth's sur face by comets and their fragments. Analysis of comets via spectrosc opic observations has identified many organic molecules, including me thane, ethane, arnmonia, cyanic acid, formaldehyde, formamide, acetal ehyde, acetonitrile, and methanol. Reactions between these identifie d molecules could allow the formation of more complex organics such a s amino acids. Isotopic analysis could reveal whether an extraterrest rial signature is present in the Stardust-exposed amines and amino ac ids. Although bulk isotopic analysis would be dominated by the EACA contaminant's terrestrial signature, compoundspecific isotope analysi s (CSIA) could determine the signature of each of the other individua l amines. Here, we report on progress made towards CSIA of the amino acids glycine and EACA in Stardustreturned samples.

  16. Isotopic analysis of Bothrops atrox in Amazonian forest

    NASA Astrophysics Data System (ADS)

    Martinez, M. G.; Silva, A. M.; Chalkidis, H.; de Oliveira Júnior, R. C.; Camargo, P. B.

    2012-12-01

    The poisoning of snakes is considered a public health problem, especially in populations from rural areas of tropical and subtropical countries. In Brazil, the 26,000 snakebites, 90% are of the genus Bothrops, and Bothrops atrox species predominant in the Amazon region including all the Brazilian Amazon. Research shows that using stable isotopes, we can verify the isotopic composition of tissues of animals that depend mainly on food, water ingested and inhaled gases. For this study, samples taken from Bothrops atrox (B. atrox), in forest using pitfall traps and fall ("Pitt-fall traps with drift fence"). The analyzes were performed by mass spectrometry, where the analytical error is 0.3‰ for carbon and 0.5‰ to nitrogen. The results of the forest animals are significantly different from results of animal vivarium. The average values of the tissues and venoms of snakes of the forest for carbon-13 and nitrogen-15 are: δ13C = -24.68‰ and δ15N = 14.22‰ and mean values of tissue and poisons snakes vivarium (Instituto Butantan) to carbon-13 and nitrogen-15 are δ13C = -20.47‰ and δ15N = 8.36‰, with a significantly different due to different sources of food animals. Based on all results isotopic δ13C and δ15N, we can suggest that changes as the power of the serpent, (nature and captivity), changes occur in relation to diet and environment as the means of the isotopic data are quite distinct, showing that these changes can also cause metabolic changes in the body of the animal itself and the different periods of turnover of each tissue analyzed.

  17. Is it really organic?--multi-isotopic analysis as a tool to discriminate between organic and conventional plants.

    PubMed

    Laursen, K H; Mihailova, A; Kelly, S D; Epov, V N; Bérail, S; Schjoerring, J K; Donard, O F X; Larsen, E H; Pedentchouk, N; Marca-Bell, A D; Halekoh, U; Olesen, J E; Husted, S

    2013-12-01

    Novel procedures for analytical authentication of organic plant products are urgently needed. Here we present the first study encompassing stable isotopes of hydrogen, carbon, nitrogen, oxygen, magnesium and sulphur as well as compound-specific nitrogen and oxygen isotope analysis of nitrate for discrimination of organically and conventionally grown plants. The study was based on wheat, barley, faba bean and potato produced in rigorously controlled long-term field trials comprising 144 experimental plots. Nitrogen isotope analysis revealed the use of animal manure, but was unable to discriminate between plants that were fertilised with synthetic nitrogen fertilisers or green manures from atmospheric nitrogen fixing legumes. This limitation was bypassed using oxygen isotope analysis of nitrate in potato tubers, while hydrogen isotope analysis allowed complete discrimination of organic and conventional wheat and barley grains. It is concluded, that multi-isotopic analysis has the potential to disclose fraudulent substitutions of organic with conventionally cultivated plants.

  18. A Nanoengineered Conductometric Device for Accurate Analysis of Elemental Mercury Vapor.

    PubMed

    Griffin, Matthew J; Kabir, K M Mohibul; Coyle, Victoria E; Kandjani, Ahmad Esmaielzadeh; Sabri, Ylias M; Ippolito, Samuel J; Bhargava, Suresh K

    2016-02-01

    We developed a novel conductometric device with nanostructured gold (Au) sensitive layer which showed high-performance for elemental mercury (Hg(0)) vapor detection under simulated conditions that resemble harsh industrial environments. That is, the Hg(0) vapor sensing performance of the developed sensor was investigated under different operating temperatures (30-130 °C) and working conditions (i.e., humid) as well as in the presence of various interfering gas species, including ammonia (NH3), hydrogen sulfide (H2S), nitric oxide (NO), carbon mono-oxide (CO), carbon dioxide (CO2), sulfur dioxide (SO2), hydrogen (H2), methane (CH4), and volatile organic compounds (VOCs) such as ethylmercaptan (EM), acetaldehyde (MeCHO) and methyl ethyl ketone (MEK) among others. The results indicate that the introduction of Au nanostructures (referred to as nanospikes) on the sensor's surface enhanced the sensitivity toward Hg(0) vapor by up-to 450%. The newly developed sensor exhibited a limit of detection (LoD) (∼35 μg/m(3)), repeatability (∼94%), desorption efficiency (100%) and selectivity (∼93%) when exposed to different concentrations of Hg(0) vapor (0.5 to 9.1 mg/m(3)) and interfering gas species at a chosen operating temperature of 105 °C. Furthermore, the sensor was also found to show 91% average selectivity when exposed toward harsher industrial gases such as NO, CO, CO2, and SO2 along with same concentrations of Hg(0) vapor in similar operating conditions. In fact, this is the first time a conductometric sensor is shown to have high selectivity toward Hg(0) vapor even in the presence of H2S. Overall results indicate that the developed sensor has immense potential to be used as accurate online Hg(0) vapor monitoring technology within industrial processes.

  19. Assessment of degradation pathways in an aquifer with mixed chlorinated hydrocarbon contamination using stable isotope analysis.

    PubMed

    Hunkeler, Daniel; Aravena, Ramon; Berry-Spark, Karen; Cox, Evan

    2005-08-15

    The demonstration of monitored natural attenuation (MNA) of chlorinated hydrocarbons in groundwater is typically conducted through the evaluation of concentration trends and parent-daughter product relationships along prevailing groundwater flow paths. Unfortunately, at sites contaminated by mixtures of chlorinated ethenes, ethanes, and methanes, the evaluation of MNA by using solely concentration data and parent-daughter relationships can result in erroneous conclusions regarding the degradation mechanisms that are truly active at the site, since many of the daughter products can be derived from multiple parent compounds. Stable carbon isotope analysis was used, in conjunction with concentration data, to clarify and confirm the active degradation pathways at a former waste solvent disposal site where at least 14 different chlorinated hydrocarbons have been detected in the groundwater. The isotope data indicate that TCE, initially believed to be present as a disposed product and/or a PCE dechlorination intermediate, is attributable to dehydrochlorination of 1,1,2,2-PCA. The isotope data further support that vinyl chloride and ethene in the site groundwater result from dichloroelimination of 1,1,2-trichlorethane and 1,2-dichloroethane, respectively, rather than from reductive dechlorination of the chlorinated ethenes PCE, TCE, or 1,2-DCE. The isotope data confirm that the chlorinated ethanes and chlorinated methanes are undergoing significant intrinsic degradation, whereas degradation of the chlorinated ethenes may be limited. In addition to the classical trend of enriched isotope values of the parent compounds with increasing distance associated to biodegradation, shifts of isotope ratios of degradation byproduct in the opposite direction due to mixing of isotopically light byproducts of biodegradation with compounds from the source are shown to be of high diagnostic value. These data underline the value of stable isotope analysis in confirming transformation

  20. Linking cases of illegal shootings of the endangered California condor using stable lead isotope analysis

    SciTech Connect

    Finkelstein, Myra E.; Kuspa, Zeka E.; Welch, Alacia; Eng, Curtis; Clark, Michael; Burnett, Joseph; Smith, Donald R.

    2014-10-15

    Lead poisoning is preventing the recovery of the critically endangered California condor (Gymnogyps californianus) and lead isotope analyses have demonstrated that ingestion of spent lead ammunition is the principal source of lead poisoning in condors. Over an 8 month period in 2009, three lead-poisoned condors were independently presented with birdshot embedded in their tissues, evidencing they had been shot. No information connecting these illegal shooting events existed and the timing of the shooting(s) was unknown. Using lead concentration and stable lead isotope analyses of feathers, blood, and recovered birdshot, we observed that: i) lead isotope ratios of embedded shot from all three birds were measurably indistinguishable from each other, suggesting a common source; ii) lead exposure histories re-constructed from feather analysis suggested that the shooting(s) occurred within the same timeframe; and iii) two of the three condors were lead poisoned from a lead source isotopically indistinguishable from the embedded birdshot, implicating ingestion of this type of birdshot as the source of poisoning. One of the condors was subsequently lead poisoned the following year from ingestion of a lead buckshot (blood lead 556 µg/dL), illustrating that ingested shot possess a substantially greater lead poisoning risk compared to embedded shot retained in tissue (blood lead ∼20 µg/dL). To our knowledge, this is the first study to use lead isotopes as a tool to retrospectively link wildlife shooting events. - Highlights: • We conducted a case-based analysis of illegal shootings of California condors. • Blood and feather Pb isotopes were used to reconstruct the illegal shooting events. • Embedded birdshot from the three condors had the same Pb isotope ratios. • Feather and blood Pb isotopes indicated that the condors were shot in a common event. • Ingested shot causes substantially greater lead exposure compared to embedded shot.

  1. Advances in Proteomics Data Analysis and Display Using an Accurate Mass and Time Tag Approach

    SciTech Connect

    Zimmer, Jennifer S.; Monroe, Matthew E.; Qian, Weijun; Smith, Richard D.

    2006-01-20

    Proteomics, and the larger field of systems biology, have recently demonstrated utility in both the understanding of cellular processes on the molecular level and the identification of potential biomarkers of various disease states. The large amount of data generated by utilizing high mass accuracy mass spectrometry for high-throughput proteomics analyses presents a challenge in data processing, analysis and display. This review focuses on recent advances in nanoLC-FTICR-MS-based proteomics analysis and the accompanying data processing tools that have been developed in order to interpret and display the large volumes of data produced.

  2. Accurate and noninvasive embryos screening during in vitro fertilization (IVF) assisted by Raman analysis of embryos culture medium Accurate and noninvasive embryos screening during IVF

    NASA Astrophysics Data System (ADS)

    Shen, A. G.; Peng, J.; Zhao, Q. H.; Su, L.; Wang, X. H.; Hu, J. M.; Yang, J.

    2012-04-01

    In combination with morphological evaluation tests, we employ Raman spectroscopy to select higher potential reproductive embryos during in vitro fertilization (IVF) based on chemical composition of embryos culture medium. In this study, 57 Raman spectra are acquired from both higher and lower quality embryos culture medium (ECM) from 10 patients which have been preliminarily confirmed by clinical assay. Data are fit by using a linear combination model of least squares method in which 12 basis spectra represent the chemical features of ECM. The final fitting coefficients provide insight into the chemical compositions of culture medium samples and are subsequently used as criterion to evaluate the quality of embryos. The relative fitting coefficients ratios of sodium pyruvate/albumin and phenylalanine/albumin seem act as key roles in the embryo screening, attaining 85.7% accuracy in comparison with clinical pregnancy. The good results demonstrate that Raman spectroscopy therefore is an important candidate for an accurate and noninvasive screening of higher quality embryos, which potentially decrease the time-consuming clinical trials during IVF.

  3. Trial application of oxygen and carbon isotope analysis in tooth enamel for identification of past-war victims for discriminating between Japanese and US soldiers.

    PubMed

    Someda, Hidetoshi; Gakuhari, Takashi; Akai, Junko; Araki, Yoshiyuki; Kodera, Tsutomu; Tsumatori, Gentaro; Kobayashi, Yasushi; Matsunaga, Satoru; Abe, Shinichi; Hashimoto, Masatsugu; Saito, Megumi; Yoneda, Minoru; Ishida, Hajime

    2016-04-01

    Stable isotope analysis has undergone rapid development in recent years and yielded significant results in the field of forensic sciences. In particular, carbon and oxygen isotopic ratios in tooth enamel obtained from human remains can provide useful information for the crosschecking of morphological and DNA analyses and facilitate rapid on-site prescreening for the identification of remains. This study analyzes carbon and oxygen isotopic ratios in the tooth enamel of Japanese people born between 1878 and 1930, in order to obtain data for methodological differentiation of Japanese and American remains from the Second World War. The carbon and oxygen isotopic ratios in the tooth enamel of the examined Japanese individuals are compared to previously reported data for American individuals (born post WWII), and statistical analysis is conducted using a discrimination method based on a logistic regression analysis. The discrimination between the Japanese and US populations, including Alaska and Hawaii, is found to be highly accurate. Thus, the present method has potential as a discrimination technique for both populations for use in the examination of mixed remains comprising Japanese and American fallen soldiers.

  4. Can Raters with Reduced Job Descriptive Information Provide Accurate Position Analysis Questionnaire (PAQ) Ratings?

    ERIC Educational Resources Information Center

    Friedman, Lee; Harvey, Robert J.

    1986-01-01

    Job-naive raters provided with job descriptive information made Position Analysis Questionnaire (PAQ) ratings which were validated against ratings of job analysts who were also job content experts. None of the reduced job descriptive information conditions enabled job-naive raters to obtain either acceptable levels of convergent validity with…

  5. How to Construct More Accurate Student Models: Comparing and Optimizing Knowledge Tracing and Performance Factor Analysis

    ERIC Educational Resources Information Center

    Gong, Yue; Beck, Joseph E.; Heffernan, Neil T.

    2011-01-01

    Student modeling is a fundamental concept applicable to a variety of intelligent tutoring systems (ITS). However, there is not a lot of practical guidance on how to construct and train such models. This paper compares two approaches for student modeling, Knowledge Tracing (KT) and Performance Factors Analysis (PFA), by evaluating their predictive…

  6. Solid rocket booster internal flow analysis by highly accurate adaptive computational methods

    NASA Technical Reports Server (NTRS)

    Huang, C. Y.; Tworzydlo, W.; Oden, J. T.; Bass, J. M.; Cullen, C.; Vadaketh, S.

    1991-01-01

    The primary objective of this project was to develop an adaptive finite element flow solver for simulating internal flows in the solid rocket booster. Described here is a unique flow simulator code for analyzing highly complex flow phenomena in the solid rocket booster. New methodologies and features incorporated into this analysis tool are described.

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

    EPA Science Inventory

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

  8. Field-based stable isotope analysis of carbon dioxide by mid-infrared laser spectroscopy for carbon capture and storage monitoring.

    PubMed

    van Geldern, Robert; Nowak, Martin E; Zimmer, Martin; Szizybalski, Alexandra; Myrttinen, Anssi; Barth, Johannes A C; Jost, Hans-Jürg

    2014-12-16

    A newly developed isotope ratio laser spectrometer for CO2 analyses has been tested during a tracer experiment at the Ketzin pilot site (northern Germany) for CO2 storage. For the experiment, 500 tons of CO2 from a natural CO2 reservoir was injected in supercritical state into the reservoir. The carbon stable isotope value (δ(13)C) of injected CO2 was significantly different from background values. In order to observe the breakthrough of the isotope tracer continuously, the new instruments were connected to a stainless steel riser tube that was installed in an observation well. The laser instrument is based on tunable laser direct absorption in the mid-infrared. The instrument recorded a continuous 10 day carbon stable isotope data set with 30 min resolution directly on-site in a field-based laboratory container during a tracer experiment. To test the instruments performance and accuracy the monitoring campaign was accompanied by daily CO2 sampling for laboratory analyses with isotope ratio mass spectrometry (IRMS). The carbon stable isotope ratios measured by conventional IRMS technique and by the new mid-infrared laser spectrometer agree remarkably well within analytical precision. This proves the capability of the new mid-infrared direct absorption technique to measure high precision and accurate real-time stable isotope data directly in the field. The laser spectroscopy data revealed for the first time a prior to this experiment unknown, intensive dynamic with fast changing δ(13)C values. The arrival pattern of the tracer suggest that the observed fluctuations were probably caused by migration along separate and distinct preferential flow paths between injection well and observation well. The short-term variances as observed in this study might have been missed during previous works that applied laboratory-based IRMS analysis. The new technique could contribute to a better tracing of the migration of the underground CO2 plume and help to ensure the long

  9. Field-based stable isotope analysis of carbon dioxide by mid-infrared laser spectroscopy for carbon capture and storage monitoring.

    PubMed

    van Geldern, Robert; Nowak, Martin E; Zimmer, Martin; Szizybalski, Alexandra; Myrttinen, Anssi; Barth, Johannes A C; Jost, Hans-Jürg

    2014-12-16

    A newly developed isotope ratio laser spectrometer for CO2 analyses has been tested during a tracer experiment at the Ketzin pilot site (northern Germany) for CO2 storage. For the experiment, 500 tons of CO2 from a natural CO2 reservoir was injected in supercritical state into the reservoir. The carbon stable isotope value (δ(13)C) of injected CO2 was significantly different from background values. In order to observe the breakthrough of the isotope tracer continuously, the new instruments were connected to a stainless steel riser tube that was installed in an observation well. The laser instrument is based on tunable laser direct absorption in the mid-infrared. The instrument recorded a continuous 10 day carbon stable isotope data set with 30 min resolution directly on-site in a field-based laboratory container during a tracer experiment. To test the instruments performance and accuracy the monitoring campaign was accompanied by daily CO2 sampling for laboratory analyses with isotope ratio mass spectrometry (IRMS). The carbon stable isotope ratios measured by conventional IRMS technique and by the new mid-infrared laser spectrometer agree remarkably well within analytical precision. This proves the capability of the new mid-infrared direct absorption technique to measure high precision and accurate real-time stable isotope data directly in the field. The laser spectroscopy data revealed for the first time a prior to this experiment unknown, intensive dynamic with fast changing δ(13)C values. The arrival pattern of the tracer suggest that the observed fluctuations were probably caused by migration along separate and distinct preferential flow paths between injection well and observation well. The short-term variances as observed in this study might have been missed during previous works that applied laboratory-based IRMS analysis. The new technique could contribute to a better tracing of the migration of the underground CO2 plume and help to ensure the long

  10. Stable isotope dilution analysis of hydrologic samples by inductively coupled plasma mass spectrometry

    USGS Publications Warehouse

    Garbarino, J.R.; Taylor, H.E.

    1987-01-01

    Inductively coupled plasma mass spectrometry is employed in the determination of Ni, Cu, Sr, Cd, Ba, Ti, and Pb in nonsaline, natural water samples by stable isotope dilution analysis. Hydrologic samples were directly analyzed without any unusual pretreatment. Interference effects related to overlapping isobars, formation of metal oxide and multiply charged ions, and matrix composition were identified and suitable methods of correction evaluated. A comparability study snowed that single-element isotope dilution analysis was only marginally better than sequential multielement isotope dilution analysis. Accuracy and precision of the single-element method were determined on the basis of results obtained for standard reference materials. The instrumental technique was shown to be ideally suited for programs associated with certification of standard reference materials.

  11. Accurate quantification of the mercapturic acids of acrylonitrile and its genotoxic metabolite cyanoethylene-epoxide in human urine by isotope-dilution LC-ESI/MS/MS.

    PubMed

    Schettgen, T; Bertram, J; Kraus, T

    2012-08-30

    Acrylonitrile is a highly important industrial chemical with a high production volume worldwide, especially in the plastics industry. It is classified as a possible human carcinogen by the International Agency for Research on Cancer (IARC group 2B). During metabolism of acrylonitrile, the genotoxic metabolite cyanoethylene-epoxide is formed. The urinary mercapturic acids of acrylonitrile, namely N-acetyl-S-(2-cyanoethyl)-L-cysteine (CEMA) and cyanoethylene-epoxide, namely N-acetyl-S-(1-cyano-2-hydroxyethyl)-L-cysteine (CHEMA) are specific biomarkers for the determination of individual internal exposure to acrylonitrile and its highly reactive metabolite. We have developed and validated a sensitive method for the accurate determination of CEMA and CHEMA in human urine with a multidimensional LC/MS/MS-method using deuterium-labelled analogues for both analytes as internal standards. Analytes were stripped from urinary matrix by online extraction on a restricted access material, transferred to the analytical column and determined by tandem mass spectrometry. The limit of quantification (LOQ) for CEMA and CHEMA was 1 μg/L urine and allowed to quantify the background exposure of the (smoking) general population. Precision within and between series for CHEMA ranged from 2.6 to 8.0% at four concentrations ranging from 8.3 to 86 μg/L urine, mean accuracy was between 94 and 100%. For CEMA, precision within and between series ranged from 2.4 to 14.5% at four concentrations ranging from 15.1 to 196 μg/L urine, mean accuracy was between 91 and 104%. We applied the method to spot urine samples of 83 subjects of the general population with no known occupational exposure to acrylonitrile. Median levels (range) for CEMA and CHEMA in urine samples of non-smokers (n=47) were 1.9 μg/L (<1-16.4 μg/L) and<1 μg/L (<1-3 μg/L), while in urine samples of smokers (n=36), median levels were 184 μg/L (2-907 μg/L) and 29.3 μg/L (<1-147 μg/L), respectively. Smokers showed a

  12. Accurate abundance analysis of late-type stars: advances in atomic physics

    NASA Astrophysics Data System (ADS)

    Barklem, Paul S.

    2016-05-01

    The measurement of stellar properties such as chemical compositions, masses and ages, through stellar spectra, is a fundamental problem in astrophysics. Progress in the understanding, calculation and measurement of atomic properties and processes relevant to the high-accuracy analysis of F-, G-, and K-type stellar spectra is reviewed, with particular emphasis on abundance analysis. This includes fundamental atomic data such as energy levels, wavelengths, and transition probabilities, as well as processes of photoionisation, collisional broadening and inelastic collisions. A recurring theme throughout the review is the interplay between theoretical atomic physics, laboratory measurements, and astrophysical modelling, all of which contribute to our understanding of atoms and atomic processes, as well as to modelling stellar spectra.

  13. Potential for using isotopically altered metalloproteins in species-specific isotope dilution analysis of proteins by HPLC coupled to inductively coupled plasma mass spectrometry.

    PubMed

    Harrington, Chris F; Vidler, Daniel S; Watts, Michael J; Hall, John F

    2005-07-01

    The production and evaluation of an isotopically enriched metalloprotein standard for use as a calibrant in species-specific isotope dilution analysis by HPLC coupled to inductively coupled plasma mass spectrometry is described. Using a model system involving the copper-containing protein rusticyanin (Rc) from the bacterium Acido-thiobacillus ferrooxidans, it was possible to demonstrate the analytical conditions that could be used for the measurement of metalloproteins by on-line IDMS analysis. Rc was chosen because it is a well-characterized protein with an established amino acid sequence and can be produced in suitable quantities using a bacterial recombinant system. Three different forms of the protein were studied by organic and inorganic mass spectrometry: the native form of the protein containing a natural isotopic profile for copper, an isotopically enriched species containing virtually all of its copper as the 65Cu isotope, and the nonmetalated apo form. Incorporation of the copper isotopes into the apo form of the protein was determined using a UV-vis spectrophotometric assay and shown to be complete for each of the copper-containing species. The experimental conditions required to maintain the conformational form of the protein with a nonexchangeable copper center were established using +ve electrospray mass spectrometry. A pH 7.0 buffer was found to afford the most appropriate conditions, and this was then used with HPLC-ICP-MS to verify the stability of the copper center by analysis of mixtures of different isotopic solutions. No exchange of the enriched copper isotope from Rc with an added naturally abundant inorganic copper cation was observed under a neutral pH environment, indicating that species-specific ID-MS analysis of metalloproteins is possible.

  14. Isotopic composition of tellurium in the Abee meteorite

    SciTech Connect

    Smith, C.L.; De Laeter, J.R.

    1986-03-01

    The research of Smith et al. (1978) and Oliver et al. (1981) on the Abee meteorite's possible negative tellurium anomaly is extended. Two sets of measurements of the tellurium isotopic composition of Abee are reported, and the meteoritic data are compared with a terrestrial tellurium standard. No isotopic anomalies can be distinguished within the error limits. However, further work on the isotopic composition of Te in residues from the Allende meteorite need to be pursued by accurate mass spectrometric analysis. 23 references

  15. Microbial degradation of alpha-cypermethrin in soil by compound-specific stable isotope analysis.

    PubMed

    Xu, Zemin; Shen, Xiaoli; Zhang, Xi-Chang; Liu, Weiping; Yang, Fangxing

    2015-09-15

    To assess microbial degradation of alpha-cypermethrin in soil, attenuation of alpha-cypermethrin was investigated by compound-specific stable isotope analysis. The variations of the residual concentrations and stable carbon isotope ratios of alpha-cypermethrin were detected in unsterilized and sterilized soils spiked with alpha-cypermethrin. After an 80 days' incubation, the concentrations of alpha-cypermethrin decreased to 0.47 and 3.41 mg/kg in the unsterilized soils spiked with 2 and 10 mg/kg, while those decreased to 1.43 and 6.61 mg/kg in the sterilized soils. Meanwhile, the carbon isotope ratios shifted to -29.14 ± 0.22‰ and -29.86 ± 0.33‰ in the unsterilized soils spiked with 2 and 10 mg/kg, respectively. The results revealed that microbial degradation contributed to the attenuation of alpha-cypermethrin and induced the carbon isotope fractionation. In order to quantitatively assess microbial degradation, a relationship between carbon isotope ratios and residual concentrations of alpha-cypermethrin was established according to Rayleigh equation. An enrichment factor, ϵ = -1.87‰ was obtained, which can be employed to assess microbial degradation of alpha-cypermethrin. The significant carbon isotope fractionation during microbial degradation suggests that CSIA is a proper approach to qualitatively detect and quantitatively assess the biodegradation during attenuation process of alpha-cypermethrin in the field.

  16. Apparatus for use in rapid and accurate controlled-potential coulometric analysis

    DOEpatents

    Frazzini, Thomas L.; Holland, Michael K.; Pietri, Charles E.; Weiss, Jon R.

    1981-01-01

    An apparatus for controlled-potential coulometric analysis of a solution includes a cell to contain the solution to be analyzed and a plurality of electrodes to contact the solution in the cell. Means are provided to stir the solution and to control the atmosphere above it. A potentiostat connected to the electrodes controls potential differences among the electrodes. An electronic circuit connected to the potentiostat provides analog-to-digital conversion and displays a precise count of charge transfer during a desired chemical process. This count provides a measure of the amount of an unknown substance in the solution.

  17. Accurate RT-qPCR gene expression analysis on cell culture lysates

    PubMed Central

    Van Peer, Gert; Mestdagh, Pieter; Vandesompele, Jo

    2012-01-01

    Gene expression quantification on cultured cells using the reverse transcription quantitative polymerase chain reaction (RT-qPCR) typically involves an RNA purification step that limits sample processing throughput and precludes parallel analysis of large numbers of samples. An approach in which cDNA synthesis is carried out on crude cell lysates instead of on purified RNA samples can offer a fast and straightforward alternative. Here, we evaluate such an approach, benchmarking Ambion's Cells-to-CT kit with the classic workflow of RNA purification and cDNA synthesis, and demonstrate its good accuracy and superior sensitivity. PMID:22355736

  18. Advances in Proteomics Data Analysis and Display Using an Accurate Mass and Time Tag Approach

    PubMed Central

    Zimmer, Jennifer S.D.; Monroe, Matthew E.; Qian, Wei-Jun; Smith, Richard D.

    2007-01-01

    Proteomics has recently demonstrated utility in understanding cellular processes on the molecular level as a component of systems biology approaches and for identifying potential biomarkers of various disease states. The large amount of data generated by utilizing high efficiency (e.g., chromatographic) separations coupled to high mass accuracy mass spectrometry for high-throughput proteomics analyses presents challenges related to data processing, analysis, and display. This review focuses on recent advances in nanoLC-FTICR-MS-based proteomics approaches and the accompanying data processing tools that have been developed to display and interpret the large volumes of data being produced. PMID:16429408

  19. Recent developments in application of stable isotope analysis on agro-product authenticity and traceability.

    PubMed

    Zhao, Yan; Zhang, Bin; Chen, Gang; Chen, Ailiang; Yang, Shuming; Ye, Zhihua

    2014-02-15

    With the globalisation of agro-product markets and convenient transportation of food across countries and continents, the potential for distribution of mis-labelled products increases accordingly, highlighting the need for measures to identify the origin of food. High quality food with identified geographic origin is a concern not only for consumers, but also for agriculture farmers, retailers and administrative authorities. Currently, stable isotope ratio analysis in combination with other chemical methods gradually becomes a promising approach for agro-product authenticity and traceability. In the last five years, a growing number of research papers have been published on tracing agro-products by stable isotope ratio analysis and techniques combining with other instruments. In these reports, the global variety of stable isotope compositions has been investigated, including light elements such as C, N, H, O and S, and heavy isotopes variation such as Sr and B. Several factors also have been considered, including the latitude, altitude, evaporation and climate conditions. In the present paper, an overview is provided on the authenticity and traceability of the agro-products from both animal and plant sources by stable isotope ratio analysis.

  20. Sr Isotope Analysis of Lacustrine Fossils Reveals Paleohydrological Reorganisation in the Turkana Basin Through the Holocene.

    NASA Astrophysics Data System (ADS)

    Vonhof, H.; Lubbe, J. V. D.; Joordens, J. J.; Feibel, C. S.; Junginger, A.; Garcin, Y.; Krause-Nehring, J.; Beck, C.; Johnson, T. C.

    2015-12-01

    Lake Turkana in northern Kenya is one of the largest lakes in the East African Rift System (EARS) that experienced significant climate-driven lake level variation over the Holocene. Arguably the most important feature of Holocene climate change in the EARS is the termination of the African Humid Period (AHP), that caused a ~70 meter lake level drop in Lake Turkana. The precise hydrological response to the termination of the AHP is potentially complex, because Lake Turkana lies at the cross roads of two large atmospheric convection systems; the Intertropical Convergence Zone (ITCZ) and the Congo Air Boundary (CAB). Shifting of these atmospheric systems around the end of the AHP dramatically rearranged spatial rainfall patterns in the Turkana Basin catchment, causing changes in relative runoff contributions from the different sub-catchments in the Turkana Basin. We here present a Holocene Turkana lake water Sr-isotope reconstruction, based on the analysis of well-dated lacustrine ostracods and shells. This reconstruction reveals consistently high Sr isotope values for the early Holocene, followed by a remarkable drop of Sr isotope ratios around the AHP termination. We interpret this pattern to represent a westward shift in the location of the CAB, leading to the reduction and eventual shutdown of runoff contribution from the Chew Bahir Basin to the Turkana Basin at the end of the AHP. The record demonstrates the exceptional suitability of Sr isotope data for this type of paleohydrological reconstructions. This is mainly due to the chemically conservative Sr-isotope mass balance in EARS lake systems, which is insensitive to environmental change at seasonal timescales that so often overprints the longer term climate signal in stable (oxygen and carbon) isotope records of these lakes. Furthermore, when Sr-isotope signatures of the contributing sub-catchments are known, the observed Sr isotope trends can be interpreted in terms of spatial shifts in climate driven runoff

  1. Compound specific isotope analysis to investigate pesticide degradation in lysimeter experiments at field conditions

    NASA Astrophysics Data System (ADS)

    Ryabenko, Evgenia; Elsner, Martin; Bakkour, Rani; Hofstetter, Thomas; Torrento, Clara; Hunkeler, Daniel

    2015-04-01

    The frequent detection of organic micropollutants such as pesticides, consumer care products or pharmaceuticals in water is an increasing concern for human and ecosystem health. Degradation analysis of these compounds can be challenging in complex systems due to the fact that metabolites are not always found and mass balances frequently cannot be closed. Many abiotic and biotic degradation pathways cause, however, distinct isotope fractionation, where light isotopes are transferred preferentially from the reactant to the product pool (normal isotope fractionation). Compound-specific isotope analysis (CSIA) of multiple elements is a particularly powerful method to evaluate organic micropollutant transformation, because it can even give pathway-specific isotope fractionation (1,2). Available CSIA field studies, however, have focused almost exclusively on volatile petroleum and chlorinated hydrocarbons, which are present in high concentrations in the environment and can be extracted easily from water for GC-IRMS analysis. In the case of micropollutants, such as pesticides, CSIA in more challenging since it needs to be conducted at lower concentrations and requires pre-concentration, purification and high chromatographic performance (3). In this study we used lysimeters experiments to analyze transformation of atrazine, acetochlor, metolachlor and chloridazone by studying associated isotope fractionation. The project combines a) analytical method development for CSIA, b) identification of pathways of micropollutant degradation and c) quantification of transformation processes under field condition. The pesticides were applied both, at the soil surface and below the top soil under field-relevant concentrations in May 2014. After typical irrigation of the lysimeters, seepage water was collected in 50L bottles and stored for further SPE and CSIA. Here we present the very first result of a) analytical method development, b) improvement of SPE methods for complex pesticide

  2. Microcalorimeter Q-spectroscopy for rapid isotopic analysis of trace actinide samples

    NASA Astrophysics Data System (ADS)

    Croce, M. P.; Bond, E. M.; Hoover, A. S.; Kunde, G. J.; Mocko, V.; Rabin, M. W.; Weisse-Bernstein, N. R.; Wolfsberg, L. E.; Bennett, D. A.; Hays-Wehle, J.; Schmidt, D. R.; Ullom, J. N.

    2015-06-01

    We are developing superconducting transition-edge sensor (TES) microcalorimeters that are optimized for rapid isotopic analysis of trace actinide samples by Q-spectroscopy. By designing mechanically robust TESs and simplified detector assembly methods, we have developed a detector for Q-spectroscopy of actinides that can be assembled in minutes. We have characterized the effects of each simplification and present the results. Finally, we show results of isotopic analysis of plutonium samples with Q-spectroscopy detectors and compare the results to mass spectrometry.

  3. Stable isotope analysis of the karst hydrological systems in the Bay of Kvarner (Croatia).

    PubMed

    Mance, D; Hunjak, T; Lenac, D; Rubinić, J; Roller-Lutz, Z

    2014-08-01

    Here we present the results of the first systematic analysis of the stable isotope composition of the karst hydrological systems in the Bay of Kvarner. Gaussian mixture modelling, time series analysis and autoregressive integrated moving average (ARIMA) modelling were applied using the stable isotope compositions of the karst groundwater. This study revealed that the recharge is dominated by winter precipitation, the dual-porosity system is dominated by baseflow, the hinterlands of the individual springs have different degrees of karstification and the springs within the Rječina River catchment have higher recharge elevations than the springs in the Bakar Bay catchment.

  4. Smartphone-Based Accurate Analysis of Retinal Vasculature towards Point-of-Care Diagnostics

    PubMed Central

    Xu, Xiayu; Ding, Wenxiang; Wang, Xuemin; Cao, Ruofan; Zhang, Maiye; Lv, Peilin; Xu, Feng

    2016-01-01

    Retinal vasculature analysis is important for the early diagnostics of various eye and systemic diseases, making it a potentially useful biomarker, especially for resource-limited regions and countries. Here we developed a smartphone-based retinal image analysis system for point-of-care diagnostics that is able to load a fundus image, segment retinal vessels, analyze individual vessel width, and store or uplink results. The proposed system was not only evaluated on widely used public databases and compared with the state-of-the-art methods, but also validated on clinical images directly acquired with a smartphone. An Android app is also developed to facilitate on-site application of the proposed methods. Both visual assessment and quantitative assessment showed that the proposed methods achieved comparable results to the state-of-the-art methods that require high-standard workstations. The proposed system holds great potential for the early diagnostics of various diseases, such as diabetic retinopathy, for resource-limited regions and countries. PMID:27698369

  5. High Resolution Melting Analysis: A Rapid and Accurate Method to Detect CALR Mutations

    PubMed Central

    Moreno, Melania; Torres, Laura; Santana-Lopez, Gonzalo; Rodriguez-Medina, Carlos; Perera, María; Bellosillo, Beatriz; de la Iglesia, Silvia; Molero, Teresa; Gomez-Casares, Maria Teresa

    2014-01-01

    Background The recent discovery of CALR mutations in essential thrombocythemia (ET) and primary myelofibrosis (PMF) patients without JAK2/MPL mutations has emerged as a relevant finding for the molecular diagnosis of these myeloproliferative neoplasms (MPN). We tested the feasibility of high-resolution melting (HRM) as a screening method for rapid detection of CALR mutations. Methods CALR was studied in wild-type JAK2/MPL patients including 34 ET, 21 persistent thrombocytosis suggestive of MPN and 98 suspected secondary thrombocytosis. CALR mutation analysis was performed through HRM and Sanger sequencing. We compared clinical features of CALR-mutated versus 45 JAK2/MPL-mutated subjects in ET. Results Nineteen samples showed distinct HRM patterns from wild-type. Of them, 18 were mutations and one a polymorphism as confirmed by direct sequencing. CALR mutations were present in 44% of ET (15/34), 14% of persistent thrombocytosis suggestive of MPN (3/21) and none of the secondary thrombocytosis (0/98). Of the 18 mutants, 9 were 52 bp deletions, 8 were 5 bp insertions and other was a complex mutation with insertion/deletion. No mutations were found after sequencing analysis of 45 samples displaying wild-type HRM curves. HRM technique was reproducible, no false positive or negative were detected and the limit of detection was of 3%. Conclusions This study establishes a sensitive, reliable and rapid HRM method to screen for the presence of CALR mutations. PMID:25068507

  6. Tritium speciation in nuclear reactor bioshield concrete and its impact on accurate analysis.

    PubMed

    Kim, Dae Ji; E Warwick, Phillip; Croudace, Ian W

    2008-07-15

    Tritium ((3)H) is produced in nuclear reactors via several neutron-induced reactions [(2)H(n, gamma)(3)H, (6)Li(n, alpha)(3)H, (10)B(n, 2alpha)(3)H, (14)N(n, (3)H)(12)C, and ternary fission (fission yield <0.01%)]. Typically, (3)H is present as tritiated water (HTO) and can become adsorbed into structural concrete from the surface inward where it will be held in a weakly bound form. However, a systematic analysis of a sequence of subsamples taken from a reactor bioshield using combustion and liquid scintillation analysis has identified two forms of (3)H, one weakly bound and one strongly bound. The strongly bound tritium, which originates from neutron capture on trace lithium ((6)Li) within mineral phases, requires temperatures in excess of 350 degrees C to achieve quantitative recovery. The weakly bound form of tritium can be liberated at significantly lower temperatures (100 degrees C) as HTO and is associated with dehydration of hydrous mineral components. Without an appreciation that two forms of tritium can exist in reactor bioshields, the (3)H content of samples may be severely underestimated using conventional analytical approaches. These findings exemplify the need to develop robust radioactive waste characterization procedures in support of nuclear decommissioning programs. PMID:18543953

  7. Tritium speciation in nuclear reactor bioshield concrete and its impact on accurate analysis.

    PubMed

    Kim, Dae Ji; E Warwick, Phillip; Croudace, Ian W

    2008-07-15

    Tritium ((3)H) is produced in nuclear reactors via several neutron-induced reactions [(2)H(n, gamma)(3)H, (6)Li(n, alpha)(3)H, (10)B(n, 2alpha)(3)H, (14)N(n, (3)H)(12)C, and ternary fission (fission yield <0.01%)]. Typically, (3)H is present as tritiated water (HTO) and can become adsorbed into structural concrete from the surface inward where it will be held in a weakly bound form. However, a systematic analysis of a sequence of subsamples taken from a reactor bioshield using combustion and liquid scintillation analysis has identified two forms of (3)H, one weakly bound and one strongly bound. The strongly bound tritium, which originates from neutron capture on trace lithium ((6)Li) within mineral phases, requires temperatures in excess of 350 degrees C to achieve quantitative recovery. The weakly bound form of tritium can be liberated at significantly lower temperatures (100 degrees C) as HTO and is associated with dehydration of hydrous mineral components. Without an appreciation that two forms of tritium can exist in reactor bioshields, the (3)H content of samples may be severely underestimated using conventional analytical approaches. These findings exemplify the need to develop robust radioactive waste characterization procedures in support of nuclear decommissioning programs.

  8. Automated system for fast and accurate analysis of SF6 injected in the surface ocean.

    PubMed

    Koo, Chul-Min; Lee, Kitack; Kim, Miok; Kim, Dae-Ok

    2005-11-01

    This paper describes an automated sampling and analysis system for the shipboard measurement of dissolved sulfur hexafluoride (SF6) in surface marine environments into which SF6 has been deliberately released. This underway system includes a gas chromatograph associated with an electron capture detector, a fast and highly efficient SF6-extraction device, a global positioning system, and a data acquisition system based on Visual Basic 6.0/C 6.0. This work is distinct from previous studies in that it quantifies the efficiency of the SF6-extraction device and its carryover effect and examines the effect of surfactant on the SF6-extraction efficiency. Measurements can be continuously performed on seawater samples taken from a seawater line installed onboard a research vessel. The system runs on an hourly cycle during which one set of four SF6 standards is measured and SF6 derived from the seawater stream is subsequently analyzed for the rest of each 1 h period. This state-of-art system was successfully used to trace a water mass carrying Cochlodinium polykrikoides, which causes harmful algal blooms (HAB) in the coastal waters of southern Korea. The successful application of this analysis system in tracing the HAB-infected water mass suggests that the SF6 detection method described in this paper will improve the quality of the future study of biogeochemical processes in the marine environment. PMID:16294883

  9. Automated system for fast and accurate analysis of SF6 injected in the surface ocean.

    PubMed

    Koo, Chul-Min; Lee, Kitack; Kim, Miok; Kim, Dae-Ok

    2005-11-01

    This paper describes an automated sampling and analysis system for the shipboard measurement of dissolved sulfur hexafluoride (SF6) in surface marine environments into which SF6 has been deliberately released. This underway system includes a gas chromatograph associated with an electron capture detector, a fast and highly efficient SF6-extraction device, a global positioning system, and a data acquisition system based on Visual Basic 6.0/C 6.0. This work is distinct from previous studies in that it quantifies the efficiency of the SF6-extraction device and its carryover effect and examines the effect of surfactant on the SF6-extraction efficiency. Measurements can be continuously performed on seawater samples taken from a seawater line installed onboard a research vessel. The system runs on an hourly cycle during which one set of four SF6 standards is measured and SF6 derived from the seawater stream is subsequently analyzed for the rest of each 1 h period. This state-of-art system was successfully used to trace a water mass carrying Cochlodinium polykrikoides, which causes harmful algal blooms (HAB) in the coastal waters of southern Korea. The successful application of this analysis system in tracing the HAB-infected water mass suggests that the SF6 detection method described in this paper will improve the quality of the future study of biogeochemical processes in the marine environment.

  10. Combining multiple regression and principal component analysis for accurate predictions for column ozone in Peninsular Malaysia

    NASA Astrophysics Data System (ADS)

    Rajab, Jasim M.; MatJafri, M. Z.; Lim, H. S.

    2013-06-01

    This study encompasses columnar ozone modelling in the peninsular Malaysia. Data of eight atmospheric parameters [air surface temperature (AST), carbon monoxide (CO), methane (CH4), water vapour (H2Ovapour), skin surface temperature (SSKT), atmosphere temperature (AT), relative humidity (RH), and mean surface pressure (MSP)] data set, retrieved from NASA's Atmospheric Infrared Sounder (AIRS), for the entire period (2003-2008) was employed to develop models to predict the value of columnar ozone (O3) in study area. The combined method, which is based on using both multiple regressions combined with principal component analysis (PCA) modelling, was used to predict columnar ozone. This combined approach was utilized to improve the prediction accuracy of columnar ozone. Separate analysis was carried out for north east monsoon (NEM) and south west monsoon (SWM) seasons. The O3 was negatively correlated with CH4, H2Ovapour, RH, and MSP, whereas it was positively correlated with CO, AST, SSKT, and AT during both the NEM and SWM season periods. Multiple regression analysis was used to fit the columnar ozone data using the atmospheric parameter's variables as predictors. A variable selection method based on high loading of varimax rotated principal components was used to acquire subsets of the predictor variables to be comprised in the linear regression model of the atmospheric parameter's variables. It was found that the increase in columnar O3 value is associated with an increase in the values of AST, SSKT, AT, and CO and with a drop in the levels of CH4, H2Ovapour, RH, and MSP. The result of fitting the best models for the columnar O3 value using eight of the independent variables gave about the same values of the R (≈0.93) and R2 (≈0.86) for both the NEM and SWM seasons. The common variables that appeared in both regression equations were SSKT, CH4 and RH, and the principal precursor of the columnar O3 value in both the NEM and SWM seasons was SSKT.

  11. Simulating Expert Clinical Comprehension: Adapting Latent Semantic Analysis to Accurately Extract Clinical Concepts from Psychiatric Narrative

    PubMed Central

    Cohen, Trevor; Blatter, Brett; Patel, Vimla

    2008-01-01

    Cognitive studies reveal that less-than-expert clinicians are less able to recognize meaningful patterns of data in clinical narratives. Accordingly, psychiatric residents early in training fail to attend to information that is relevant to diagnosis and the assessment of dangerousness. This manuscript presents cognitively motivated methodology for the simulation of expert ability to organize relevant findings supporting intermediate diagnostic hypotheses. Latent Semantic Analysis is used to generate a semantic space from which meaningful associations between psychiatric terms are derived. Diagnostically meaningful clusters are modeled as geometric structures within this space and compared to elements of psychiatric narrative text using semantic distance measures. A learning algorithm is defined that alters components of these geometric structures in response to labeled training data. Extraction and classification of relevant text segments is evaluated against expert annotation, with system-rater agreement approximating rater-rater agreement. A range of biomedical informatics applications for these methods are suggested. PMID:18455483

  12. Computer-implemented system and method for automated and highly accurate plaque analysis, reporting, and visualization

    NASA Technical Reports Server (NTRS)

    Kemp, James Herbert (Inventor); Talukder, Ashit (Inventor); Lambert, James (Inventor); Lam, Raymond (Inventor)

    2008-01-01

    A computer-implemented system and method of intra-oral analysis for measuring plaque removal is disclosed. The system includes hardware for real-time image acquisition and software to store the acquired images on a patient-by-patient basis. The system implements algorithms to segment teeth of interest from surrounding gum, and uses a real-time image-based morphing procedure to automatically overlay a grid onto each segmented tooth. Pattern recognition methods are used to classify plaque from surrounding gum and enamel, while ignoring glare effects due to the reflection of camera light and ambient light from enamel regions. The system integrates these components into a single software suite with an easy-to-use graphical user interface (GUI) that allows users to do an end-to-end run of a patient record, including tooth segmentation of all teeth, grid morphing of each segmented tooth, and plaque classification of each tooth image.

  13. Quantum analysis of a bandpass Purcell filter for accurate qubit readout

    NASA Astrophysics Data System (ADS)

    Sete, Eyob A.; Martinis, John M.; Korotkov, Alexander N.

    2015-03-01

    In a circuit QED setup the readout fidelity of a superconducting qubit is partially limited by the qubit relaxation through the resonator into a transmission line, which is also known as the Purcell effect. One way to suppress this effect is to employ a filter, which impedes microwave propagation at the qubit frequency. We present a quantum analysis for the bandpass Purcell filter that was recently realized by E. Jeffrey et al. [1]. Using experimental parameters, we show that the bandpass filter suppresses the qubit relaxation rate by two orders of magnitude while keeping the measurement rate the same. We also show that in the presence of a microwave drive the qubit relaxation rate further decreases with increasing drive strength.

  14. Restriction Site Tiling Analysis: accurate discovery and quantitative genotyping of genome-wide polymorphisms using nucleotide arrays

    PubMed Central

    2010-01-01

    High-throughput genotype data can be used to identify genes important for local adaptation in wild populations, phenotypes in lab stocks, or disease-related traits in human medicine. Here we advance microarray-based genotyping for population genomics with Restriction Site Tiling Analysis. The approach simultaneously discovers polymorphisms and provides quantitative genotype data at 10,000s of loci. It is highly accurate and free from ascertainment bias. We apply the approach to uncover genomic differentiation in the purple sea urchin. PMID:20403197

  15. Compound specific 13C- and 18O-isotope analysis of organic aerosols

    NASA Astrophysics Data System (ADS)

    Blees, Jan; Saurer, Matthias; Siegwolf, Rolf T. W.; Dommen, Josef; Baltensperger, Urs

    2014-05-01

    The wide ranging environmental and health effects of aerosols are increasingly coming to light. Various studies have further highlighted the complex nature of organic aerosols, particularly oxidised organics with multiple functional groups. Source apportionment studies on aerosols are crucial to successful implementation of mitigation strategies, but this is complicated by their complex nature. Ideally, individual components of aerosols can be tracked from their source to their atmospheric sink. However, chemical alteration and the formation of secondary aerosols in the atmosphere often preclude this direct tracking on a compound specific basis. Compound specific isotope analysis could overcome these problems, as certain processes and sources impose characteristic isotope ratios on products, which may be retained even after chemical alteration in the atmosphere. Progress has been made over the past decades in the separation and identification of individual compounds that contribute to aerosol formation. Compound separation by gas chromatography (GC), coupled to mass spectrometry (MS), has enabled identification of organic compounds of various sources. On the other hand, only few studies have addressed the isotopic composition of these compounds. For successful isotopic analysis of specific compounds, using GC coupled to isotope ratio MS (GC-irMS), several challenges must be faced that go beyond the requirements for GC-MS-based compound identification. Sample extraction and handling techniques must avoid isotope fractionation. This is especially important in the light of sample extraction by e.g. thermal desorption, which may impose a temperature-induced fractionation on complex organics. Furthermore, derivatisation techniques, necessary for adequate GC compound separation, must not lead to exchange reactions of the element of interest, which would alter the measured isotope ratio. So far most studies have dealt with carbon, and other elements have been neglected

  16. Essentials of iron, chromium, and calcium isotope analysis of natural materials by thermal ionization mass spectrometry

    USGS Publications Warehouse

    Fantle, M.S.; Bullen, T.D.

    2009-01-01

    The use of isotopes to understand the behavior of metals in geological, hydrological, and biological systems has rapidly expanded in recent years. One of the mass spectrometric techniques used to analyze metal isotopes is thermal ionization mass spectrometry, or TIMS. While TIMS has been a useful analytical technique for the measurement of isotopic composition for decades and TIMS instruments are widely distributed, there are significant difficulties associated with using TIMS to analyze isotopes of the lighter alkaline earth elements and transition metals. Overcoming these difficulties to produce relatively long-lived and stable ion beams from microgram-sized samples is a non-trivial task. We focus here on TIMS analysis of three geologically and environmentally important elements (Fe, Cr, and Ca) and present an in-depth look at several key aspects that we feel have the greatest potential to trouble new users. Our discussion includes accessible descriptions of different analytical approaches and issues, including filament loading procedures, collector cup configurations, peak shapes and interferences, and the use of isotopic double spikes and related error estimation. Building on previous work, we present quantitative simulations, applied specifically in this study to Fe and Ca, that explore the effects of (1) time-variable evaporation of isotopically homogeneous spots from a filament and (2) interferences on the isotope ratios derived from a double spike subtraction routine. We discuss how and to what extent interferences at spike masses, as well as at other measured masses, affect the double spike-subtracted isotope ratio of interest (44Ca/40Ca in the case presented, though a similar analysis can be used to evaluate 56Fe/54Fe and 53Cr/52Cr). The conclusions of these simulations are neither intuitive nor immediately obvious, making this examination useful for those who are developing new methodologies. While all simulations are carried out in the context of a

  17. Wind effect on PV module temperature: Analysis of different techniques for an accurate estimation.

    NASA Astrophysics Data System (ADS)

    Schwingshackl, Clemens; Petitta, Marcello; Ernst Wagner, Jochen; Belluardo, Giorgio; Moser, David; Castelli, Mariapina; Zebisch, Marc; Tetzlaff, Anke

    2013-04-01

    In this abstract a study on the influence of wind to model the PV module temperature is presented. This study is carried out in the framework of the PV-Alps INTERREG project in which the potential of different photovoltaic technologies is analysed for alpine regions. The PV module temperature depends on different parameters, such as ambient temperature, irradiance, wind speed and PV technology [1]. In most models, a very simple approach is used, where the PV module temperature is calculated from NOCT (nominal operating cell temperature), ambient temperature and irradiance alone [2]. In this study the influence of wind speed on the PV module temperature was investigated. First, different approaches suggested by various authors were tested [1], [2], [3], [4], [5]. For our analysis, temperature, irradiance and wind data from a PV test facility at the airport Bolzano (South Tyrol, Italy) from the EURAC Institute of Renewable Energies were used. The PV module temperature was calculated with different models and compared to the measured PV module temperature at the single panels. The best results were achieved with the approach suggested by Skoplaki et al. [1]. Preliminary results indicate that for all PV technologies which were tested (monocrystalline, amorphous, microcrystalline and polycrystalline silicon and cadmium telluride), modelled and measured PV module temperatures show a higher agreement (RMSE about 3-4 K) compared to standard approaches in which wind is not considered. For further investigation the in-situ measured wind velocities were replaced with wind data from numerical weather forecast models (ECMWF, reanalysis fields). Our results show that the PV module temperature calculated with wind data from ECMWF is still in very good agreement with the measured one (R² > 0.9 for all technologies). Compared to the previous analysis, we find comparable mean values and an increasing standard deviation. These results open a promising approach for PV module

  18. [Meta-analysis of stable carbon and nitrogen isotopic enrichment factors for aquatic animals].

    PubMed

    Guo, Liang; Sun, Cui-ping; Ren, Wei-zheng; Zhang, Jian; Tang, Jian-iun; Hu, Liana-liang; Chen, Xin

    2016-02-01

    Isotopic enrichment factor (Δ, the difference between the δ value of food and a consumer tissue) is an important parameter in using stable isotope analysis (SIA) to reconstruct diets, characterize trophic relationships, elucidate patterns of resource allocation, and construct food webs. Isotopic enrichment factor has been considered as a constancy value across a broad range of animals. However, recent studies showed that the isotopic enrichment factor differed among various types of animals although the magnitude of variation was not clear. Here, we conducted a meta-analysis to synthesize and compare Δ13C and Δ15N among four types of aquatic animals (teleosts, crustaceans, reptiles and molluscs). We searched for papers published before 2014 on Web of Science and CNKI using the key words "stable isotope or isotopic fractionation or fractionation factor or isotopic enrichment or trophic enrichment". Forty-two publications that contain 140 studies on Δ13C and 159 studies on Δ15N were obtained. We conducted three parallel meta-analyses by using three types of weights (the reciprocal of variance as weights, the sample size as weights, and equal weights). The results showed that no significant difference in Δ13C among different animal types (teleosts 1.0 per thousand, crustaceans 1.3 per thousand, reptiles 0.5 per thousand, and molluscs 1.5 per thousand), while Δ15N values were significantly different (teleosts 2.4 per thousand, crustaceans 3.6 per thousand, reptiles 1.0 per thousand and molluscs 2.5 per thousand). Our results suggested that the overall mean of Δ13C could be used as a general enrichment factor, but Δ15N should be chosen according to the type of aquatic animals in using SIA to analyze trophic relationships, patterns of resource allocation and food webs. PMID:27396136

  19. [Meta-analysis of stable carbon and nitrogen isotopic enrichment factors for aquatic animals].

    PubMed

    Guo, Liang; Sun, Cui-ping; Ren, Wei-zheng; Zhang, Jian; Tang, Jian-iun; Hu, Liana-liang; Chen, Xin

    2016-02-01

    Isotopic enrichment factor (Δ, the difference between the δ value of food and a consumer tissue) is an important parameter in using stable isotope analysis (SIA) to reconstruct diets, characterize trophic relationships, elucidate patterns of resource allocation, and construct food webs. Isotopic enrichment factor has been considered as a constancy value across a broad range of animals. However, recent studies showed that the isotopic enrichment factor differed among various types of animals although the magnitude of variation was not clear. Here, we conducted a meta-analysis to synthesize and compare Δ13C and Δ15N among four types of aquatic animals (teleosts, crustaceans, reptiles and molluscs). We searched for papers published before 2014 on Web of Science and CNKI using the key words "stable isotope or isotopic fractionation or fractionation factor or isotopic enrichment or trophic enrichment". Forty-two publications that contain 140 studies on Δ13C and 159 studies on Δ15N were obtained. We conducted three parallel meta-analyses by using three types of weights (the reciprocal of variance as weights, the sample size as weights, and equal weights). The results showed that no significant difference in Δ13C among different animal types (teleosts 1.0 per thousand, crustaceans 1.3 per thousand, reptiles 0.5 per thousand, and molluscs 1.5 per thousand), while Δ15N values were significantly different (teleosts 2.4 per thousand, crustaceans 3.6 per thousand, reptiles 1.0 per thousand and molluscs 2.5 per thousand). Our results suggested that the overall mean of Δ13C could be used as a general enrichment factor, but Δ15N should be chosen according to the type of aquatic animals in using SIA to analyze trophic relationships, patterns of resource allocation and food webs.

  20. Isotopic composition analysis and age dating of uranium samples by high resolution gamma ray spectrometry

    NASA Astrophysics Data System (ADS)

    Apostol, A. I.; Pantelica, A.; Sima, O.; Fugaru, V.

    2016-09-01

    Non-destructive methods were applied to determine the isotopic composition and the time elapsed since last chemical purification of nine uranium samples. The applied methods are based on measuring gamma and X radiations of uranium samples by high resolution low energy gamma spectrometric system with planar high purity germanium detector and low background gamma spectrometric system with coaxial high purity germanium detector. The "Multigroup γ-ray Analysis Method for Uranium" (MGAU) code was used for the precise determination of samples' isotopic composition. The age of the samples was determined from the isotopic ratio 214Bi/234U. This ratio was calculated from the analyzed spectra of each uranium sample, using relative detection efficiency. Special attention is paid to the coincidence summing corrections that have to be taken into account when performing this type of analysis. In addition, an alternative approach for the age determination using full energy peak efficiencies obtained by Monte Carlo simulations with the GESPECOR code is described.

  1. First stable isotope analysis of Asiatic wild ass tail hair from the Mongolian Gobi

    PubMed Central

    Horacek, Micha; Sturm, Martina Burnik; Kaczensky, Petra

    2015-01-01

    Stable isotope analysis has become a powerful tool to study feeding ecology, water use or movement pattern in contemporary, historic and ancient species. Certain hair and teeth grow continuously, and when sampled longitudinally can provide temporally explicit information on dietary regime and movement pattern. In an initial trial, we analysed a tail sample of an Asiatic wild ass (Equus hemionus) from the Mongolian Gobi. We found seasonal variations in H, C and N isotope patterns, likely being the result of temporal variations in available feeds, water supply and possibly physiological status. Thus stable isotope analysis shows promise to study the comparative ecology of the three autochthonous equid species in the Mongolian Gobi. PMID:26339116

  2. Accurate analysis of taurine, anserine, carnosine and free amino acids in a cattle muscle biopsy sample.

    PubMed

    Imanari, Mai; Higuchi, Mikito; Shiba, Nobuya; Watanabe, Akira

    2010-06-01

    We have established an analysis method for some free amino acids (FAAs), as well as taurine (Tau), anserine (Ans) and carnosine (Car), in a fresh biopsy sample from cattle muscle. A series of model biopsy samples, corresponding to the mixtures of lean meat, fat and connective tissue, was prepared and showed high correlation coefficients between the compound concentration and the 3-methylhistidine (3-MeHis) content derived from hydrolysis of the biopsy sample (r = 0.74-0.95, P < 0.01). Interference from blood contamination could not be neglected, because the concentration of some FAAs in blood was comparable to that in muscle. However, it was possible to control the contamination of Tau, Ans, Car, glutamic acid, glutamine, asparatic acid and alanine to less than 5.0% when the blood contamination was controlled to less than 23%.These results suggest the necessity of measuring 3-MeHis as an index of lean meat and hemoglobin as an index of blood contamination when compounds in muscle biopsy samples are evaluated. We have carried out a series of these analyses using one biopsy sample and reveal differences in Tau, Ans, Car and some FAAs in beef muscle after different feeding regimes.

  3. Photo-detachment signal analysis to accurately determine electronegativity, electron temperature, and charged species density

    NASA Astrophysics Data System (ADS)

    Oudini, N.; Sirse, N.; Taccogna, F.; Ellingboe, A. R.; Bendib, A.

    2016-09-01

    Laser pulse induced photo-detachment combined with Langmuir probing has been introduced to diagnose plasma electronegativity. This technique uses a laser pulse to convert negative ions into electron-atom pairs and tracks the change of electron saturation current by a Langmuir probe. The existing model determines plasma electronegativity as the ratio of electron saturation current before and after detachment. However, this model depends on various assumptions and neglects the formation of a potential barrier between the laser channel and surrounding electronegative plasma. In this letter, we present a new analytical model to analyze photo-detachment signals in order to improve the accuracy of electronegativity measurements and extend this technique for measuring electron temperature and charged species density. This analytical model is supported by Particle-In-Cell simulation of electronegative plasma dynamics following laser photo-detachment. The analysis of the signal, detected on a simulated probe, shows that the present analytical model determines electronegativity, electron temperature, and plasma density with a relative error of ˜20%, ˜20%, and ˜50%, respectively, whereas the electronegativity obtained from a previous model is underestimated by an order of magnitude.

  4. A Cost-Benefit and Accurate Method for Assessing Microalbuminuria: Single versus Frequent Urine Analysis

    PubMed Central

    Hemmati, Roholla; Gharipour, Mojgan; Khosravi, Alireza; Jozan, Mahnaz

    2013-01-01

    Background. The purpose of this study was to answer the question whether a single testing for microalbuminuria results in a reliable conclusion leading costs saving. Methods. This current cross-sectional study included a total of 126 consecutive persons. Microalbuminuria was assessed by collection of two fasting random urine specimens on arrival to the clinic as well as one week later in the morning. Results. In overall, 17 out of 126 participants suffered from microalbuminuria that, among them, 12 subjects were also diagnosed as microalbuminuria once assessing this factor with a sensitivity of 70.6%, a specificity of 100%, a PPV of 100%, a NPV of 95.6%, and an accuracy of 96.0%. The measured sensitivity, specificity, PVV, NPV, and accuracy in hypertensive patients were 73.3%, 100%, 100%, 94.8%, and 95.5%, respectively. Also, these rates in nonhypertensive groups were 50.0%, 100%, 100%, 97.3%, and 97.4%, respectively. According to the ROC curve analysis, a single measurement of UACR had a high value for discriminating defected from normal renal function state (c = 0.989). Urinary albumin concentration in a single measurement had also high discriminative value for diagnosis of damaged kidney (c = 0.995). Conclusion. The single testing of both UACR and urine albumin level rather frequent testing leads to high diagnostic sensitivity, specificity, and accuracy as well as high predictive values in total population and also in hypertensive subgroups. PMID:24455207

  5. Borehole flowmeter logging for the accurate design and analysis of tracer tests.

    PubMed

    Basiricò, Stefano; Crosta, Giovanni B; Frattini, Paolo; Villa, Alberto; Godio, Alberto

    2015-04-01

    Tracer tests often give ambiguous interpretations that may be due to the erroneous location of sampling points and/or the lack of flow rate measurements through the sampler. To obtain more reliable tracer test results, we propose a methodology that optimizes the design and analysis of tracer tests in a cross borehole mode by using vertical borehole flow rate measurements. Experiments using this approach, herein defined as the Bh-flow tracer test, have been performed by implementing three sequential steps: (1) single-hole flowmeter test, (2) cross-hole flowmeter test, and (3) tracer test. At the experimental site, core logging, pumping tests, and static water-level measurements were previously carried out to determine stratigraphy, fracture characteristics, and bulk hydraulic conductivity. Single-hole flowmeter testing makes it possible to detect the presence of vertical flows as well as inflow and outflow zones, whereas cross-hole flowmeter testing detects the presence of connections along sets of flow conduits or discontinuities intercepted by boreholes. Finally, the specific pathways and rates of groundwater flow through selected flowpaths are determined by tracer testing. We conclude that the combined use of single and cross-borehole flowmeter tests is fundamental to the formulation of the tracer test strategy and interpretation of the tracer test results. PMID:25417730

  6. SMRT Sequencing for Parallel Analysis of Multiple Targets and Accurate SNP Phasing

    PubMed Central

    Guo, Xiaoge; Lehner, Kevin; O’Connell, Karen; Zhang, Jenny; Dave, Sandeep S.; Jinks-Robertson, Sue

    2015-01-01

    Single-molecule real-time (SMRT) sequencing generates much longer reads than other widely used next-generation (next-gen) sequencing methods, but its application to whole genome/exome analysis has been limited. Here, we describe the use of SMRT sequencing coupled with barcoding to simultaneously analyze one or a small number of genomic targets derived from multiple sources. In the budding yeast system, SMRT sequencing was used to analyze strand-exchange intermediates generated during mitotic recombination and to analyze genetic changes in a forward mutation assay. The general barcoding-SMRT approach was then extended to diffuse large B-cell lymphoma primary tumors and cell lines, where detected changes agreed with prior Illumina exome sequencing. A distinct advantage afforded by SMRT sequencing over other next-gen methods is that it immediately provides the linkage relationships between SNPs in the target segment sequenced. The strength of our approach for mutation/recombination studies (as well as linkage identification) derives from its inherent computational simplicity coupled with a lack of reliance on sophisticated statistical analyses. PMID:26497143

  7. Kinetic isotope effect of the {sup 16}O + {sup 36}O{sub 2} and {sup 18}O + {sup 32}O{sub 2} isotope exchange reactions: Dominant role of reactive resonances revealed by an accurate time-dependent quantum wavepacket study

    SciTech Connect

    Sun, Zhigang Yu, Dequan; Xie, Wenbo; Hou, Jiayi; Dawes, Richard; Guo, Hua

    2015-05-07

    The O + O{sub 2} isotope exchange reactions play an important role in determining the oxygen isotopic composition of a number of trace gases in the atmosphere, and their temperature dependence and kinetic isotope effects (KIEs) provide important constraints on our understanding of the origin and mechanism of these and other unusual oxygen KIEs important in the atmosphere. This work reports a quantum dynamics study of the title reactions on the newly constructed Dawes-Lolur-Li-Jiang-Guo (DLLJG) potential energy surface (PES). The thermal reaction rate coefficients of both the {sup 18}O + {sup 32}O{sub 2} and {sup 16}O + {sup 36}O{sub 2} reactions obtained using the DLLJG PES exhibit a clear negative temperature dependence, in sharp contrast with the positive temperature dependence obtained using the earlier modified Siebert-Schinke-Bittererova (mSSB) PES. In addition, the calculated KIE shows an improved agreement with the experiment. These results strongly support the absence of the “reef” structure in the entrance/exit channels of the DLLJG PES, which is present in the mSSB PES. The quantum dynamics results on both PESs attribute the marked KIE to strong near-threshold reactive resonances, presumably stemming from the mass differences and/or zero point energy difference between the diatomic reactant and product. The accurate characterization of the reactivity for these near-thermoneutral reactions immediately above the reaction threshold is important for correct characterization of the thermal reaction rate coefficients.

  8. Monitoring of the aerobe biodegradation of chlorinated organic solvents by stable isotope analysis

    NASA Astrophysics Data System (ADS)

    Horváth, Anikó; Futó, István; Palcsu, László

    2014-05-01

    Our chemical-biological basic research aims to eliminate chlorinated environmental contaminants from aquifers around industrial areas in the frame of research program supported by the European Social Fund (TÁMOP-4.2.2.A-11/1/KONV-2012-0043). The most careful and simplest way includes the in situ biodegradation with the help of cultured and compound specific strains. Numerous members of Pseudomonas bacteria are famous about function of bioremediation. They can metabolism the environmental hazardous chemicals like gas oils, dyes, and organic solvents. Our research based on the Pseudomonas putida F1 strain, because its ability to degrade halogenated hydrocarbons such as trichloroethylene. Several methods were investigated to estimate the rate of biodegradation, such as the measurement of the concentration of the pollutant along the contamination pathway, the microcosm's studies or the compound specific stable isotope analysis. In this area in the Transcarpathian basin we are pioneers in the stable isotope monitoring of biodegradation. The main goal is to find stable isotope fractionation factors by stable isotope analysis, which can help us to estimate the rate and effectiveness of the biodegradation. The subsequent research period includes the investigation of the method, testing its feasibility and adaptation in the environment. Last but not least, the research gives an opportunity to identify the producer of the contaminant based on the stable isotope composition of the contaminant.

  9. Tracing combustion-derived atmospheric pollutants using compound-specific isotope analysis

    NASA Astrophysics Data System (ADS)

    Ballentine, Donna Christine

    1997-04-01

    The use of compound specific carbon isotopic analysis (CSIA) has been investigated as a means to trace the origin and fate of organic pollutants in the atmosphere. Polycyclic aromatic hydrocarbons (PAH) and fatty acids have been suggested as two chemical classes which may serve as suitable molecular markers for anthropogenic combustion processes, such as fossil fuel combustion and biomass burning, that introduce significant quantities of organic pollutants into the atmospheric environment. First, analytical procedures for the extraction and isolation of these compounds from particulate aerosols, as well as a description of the isotopic measurement techniques, have been presented. Second, the precision and accuracy of these methods and measurements have been demonstrated. Third, the isotopic variability of PAH and fatty acids produced from different combustion processes has been investigated. In addition, in order to demonstrate the applicability of this technique as a means to monitor the fate of atmospheric pollutants, isotopic measurements of PAH, fatty acids, and alkanes isolated from a series of ambient aerosol samples have been made in a preliminary attempt to determine if compound specific isotope analysis of molecular markers in aerosols can be used in conjunction with other chemical and atmospheric data in order to reflect the transport of pollution episodes.

  10. Whole-Genome Sequencing Analysis Accurately Predicts Antimicrobial Resistance Phenotypes in Campylobacter spp.

    PubMed Central

    Tyson, G. H.; Chen, Y.; Li, C.; Mukherjee, S.; Young, S.; Lam, C.; Folster, J. P.; Whichard, J. M.; McDermott, P. F.

    2015-01-01

    The objectives of this study were to identify antimicrobial resistance genotypes for Campylobacter and to evaluate the correlation between resistance phenotypes and genotypes using in vitro antimicrobial susceptibility testing and whole-genome sequencing (WGS). A total of 114 Campylobacter species isolates (82 C. coli and 32 C. jejuni) obtained from 2000 to 2013 from humans, retail meats, and cecal samples from food production animals in the United States as part of the National Antimicrobial Resistance Monitoring System were selected for study. Resistance phenotypes were determined using broth microdilution of nine antimicrobials. Genomic DNA was sequenced using the Illumina MiSeq platform, and resistance genotypes were identified using assembled WGS sequences through blastx analysis. Eighteen resistance genes, including tet(O), blaOXA-61, catA, lnu(C), aph(2″)-Ib, aph(2″)-Ic, aph(2′)-If, aph(2″)-Ig, aph(2″)-Ih, aac(6′)-Ie-aph(2″)-Ia, aac(6′)-Ie-aph(2″)-If, aac(6′)-Im, aadE, sat4, ant(6′), aad9, aph(3′)-Ic, and aph(3′)-IIIa, and mutations in two housekeeping genes (gyrA and 23S rRNA) were identified. There was a high degree of correlation between phenotypic resistance to a given drug and the presence of one or more corresponding resistance genes. Phenotypic and genotypic correlation was 100% for tetracycline, ciprofloxacin/nalidixic acid, and erythromycin, and correlations ranged from 95.4% to 98.7% for gentamicin, azithromycin, clindamycin, and telithromycin. All isolates were susceptible to florfenicol, and no genes associated with florfenicol resistance were detected. There was a strong correlation (99.2%) between resistance genotypes and phenotypes, suggesting that WGS is a reliable indicator of resistance to the nine antimicrobial agents assayed in this study. WGS has the potential to be a powerful tool for antimicrobial resistance surveillance programs. PMID:26519386

  11. Isotopic analysis of uranium in natural waters by alpha spectrometry

    USGS Publications Warehouse

    Edwards, K.W.

    1968-01-01

    A method is described for the determination of U234/U238 activity ratios for uranium present in natural waters. The uranium is coprecipitated from solution with aluminum phosphate, extracted into ethyl acetate, further purified by ion exchange, and finally electroplated on a titanium disc for counting. The individual isotopes are determined by measurement of the alpha-particle energy spectrum using a high resolution low-background alpha spectrometer. Overall chemical recovery of about 90 percent and a counting efficiency of 25 percent allow analyses of water samples containing as little as 0.10 ?g/l of uranium. The accuracy of the method is limited, on most samples, primarily by counting statistics.

  12. Isotope dilution mass spectrometry for quantitative elemental analysis of powdered samples by radiofrequency pulsed glow discharge time of flight mass spectrometry.

    PubMed

    Alvarez-Toral, Aitor; Fernandez, Beatriz; Malherbe, Julien; Claverie, Fanny; Molloy, John L; Pereiro, Rosario; Sanz-Medel, Alfredo

    2013-10-15

    In recent years particular effort is being devoted to the development of pulsed glow discharges (PGDs) for mass spectrometry because this powering operation mode could offer important ionization analytical advantages. However, the capabilities of radiofrequency (RF) PGD coupled to a time of flight mass spectrometry (ToFMS) for accurate isotope ratio measurements have not been demonstrated yet. This work is focused on investigating different time positions along the pulse profile for the accurate measurement of isotope ratios. As a result, a method has been developed for the direct and simultaneous multielement determination of trace elements in powdered geological samples by RF-PGD-ToFMS in combination with isotope dilution mass spectrometry (IDMS) as an absolute measurement method directly traceable to the International System of Units. Optimized operating conditions were 70 W of applied radiofrequency power, 250 Pa of pressure, 2 ms of pulse width and 4 ms of pulse period, being argon the plasma gas used. To homogeneously distribute the added isotopically-enriched standards, lithium borate fusion of powdered solid samples was used as sample preparation approach. In this way, Cu, Zn, Ba and Pb were successfully determined by RF-PGD-ToF(IDMS) in two NIST Standard Reference Materials (SRM 2586 and SRM 2780) representing two different matrices of geological interest (soil and rock samples). Cu, Zn, Ba and Pb concentrations determined by RF-PGD-ToF(IDMS) were well in agreement with the certified values at 95% confidence interval and precisions below 12% relative standard deviation were observed for three independent analyses. Elemental concentrations investigated were in the range of 81-5770 mg/kg, demonstrating the potential of RF-PGD-ToF(IDMS) for a sensitive, accurate and robust analysis of powdered samples.

  13. Isotope dilution mass spectrometry for quantitative elemental analysis of powdered samples by radiofrequency pulsed glow discharge time of flight mass spectrometry.

    PubMed

    Alvarez-Toral, Aitor; Fernandez, Beatriz; Malherbe, Julien; Claverie, Fanny; Molloy, John L; Pereiro, Rosario; Sanz-Medel, Alfredo

    2013-10-15

    In recent years particular effort is being devoted to the development of pulsed glow discharges (PGDs) for mass spectrometry because this powering operation mode could offer important ionization analytical advantages. However, the capabilities of radiofrequency (RF) PGD coupled to a time of flight mass spectrometry (ToFMS) for accurate isotope ratio measurements have not been demonstrated yet. This work is focused on investigating different time positions along the pulse profile for the accurate measurement of isotope ratios. As a result, a method has been developed for the direct and simultaneous multielement determination of trace elements in powdered geological samples by RF-PGD-ToFMS in combination with isotope dilution mass spectrometry (IDMS) as an absolute measurement method directly traceable to the International System of Units. Optimized operating conditions were 70 W of applied radiofrequency power, 250 Pa of pressure, 2 ms of pulse width and 4 ms of pulse period, being argon the plasma gas used. To homogeneously distribute the added isotopically-enriched standards, lithium borate fusion of powdered solid samples was used as sample preparation approach. In this way, Cu, Zn, Ba and Pb were successfully determined by RF-PGD-ToF(IDMS) in two NIST Standard Reference Materials (SRM 2586 and SRM 2780) representing two different matrices of geological interest (soil and rock samples). Cu, Zn, Ba and Pb concentrations determined by RF-PGD-ToF(IDMS) were well in agreement with the certified values at 95% confidence interval and precisions below 12% relative standard deviation were observed for three independent analyses. Elemental concentrations investigated were in the range of 81-5770 mg/kg, demonstrating the potential of RF-PGD-ToF(IDMS) for a sensitive, accurate and robust analysis of powdered samples. PMID:24054645

  14. Sources and Transformations of Nitrate from Streams Draining Varying Land Uses: Evidence from Dual Isotope Analysis

    NASA Astrophysics Data System (ADS)

    Burns, D. A.; Boyer, E. W.; Elliott, E. M.; Kendall, C.

    2008-12-01

    Dual isotope analysis revealed evidence of varying sources and processes that affect the transport of nitrate (NO3-) in six watersheds of different land uses in New York. Samples from two streams draining forested watersheds indicated that NO3- derived from nitrification was dominant at baseflow. Values of δ18ONO3 were greater than previously measured in forested watersheds in this region, a difference attributed to a new, more accurate sample preparation method. A watershed dominated by suburban land use, but with all waste water discharged outside the watershed had three δ18ONO3 values > 25‰ indicating a large direct contribution of atmospheric NO3- transported to the stream during some high flow periods. Two watersheds with large proportions of agricultural land use had many samples with δ15NNO3 > 9‰ suggesting a waste source consistent with direct application of manure to fields associated with dairy farming practices in the region. These data showed a linear seasonal pattern with a δ15NNO3:δ18ONO3 close to 1:2 consistent with seasonally-varying denitrification that peaked in late summer to early fall with the warmest temperatures and lowest streamflow of the year. The large annual range of δ18ONO3 (~ 10‰) in these streams suggests a large fractionation associated with denitrification, indicative of a dominance of denitrification outside of the stream environment. Mixing of two or more NO3- sources may also have affected the patterns observed in these two agricultural streams. At a larger basin scale in a mixed land use watershed that represented the average proportions of land uses in this study, none of the source and process patterns observed in the small streams were evident. These results emphasize that observations at small to medium size watersheds of a few to several hundred km2 may be necessary to adequately quantify the relative roles of various NO3- transport and process patterns that contribute to streamflow in large basins.

  15. Tropical Silurian Paleotemperatures from Clumped Isotope Analysis of Coexisting Dolomite and Calcite

    NASA Astrophysics Data System (ADS)

    Winkelstern, I. Z.; Lohmann, K. C.

    2013-12-01

    In many instances, pervasive diagenetic alteration of original material prevents the use of quantitative climate proxies on Paleozoic or older rocks. As an inherently diagenetic phase, dolomite may provide a more resilient paleotemperature resource. The Δ47 carbonate clumped isotope thermometer has been shown to be an accurate paleothermometer and, in a limited way, has been shown to be applicable to dolomites. The shallow water carbonates of the Pipe Creek Jr. Reef in central Indiana offer an opportunity to test the viability of the technique in ancient dolomite. After formation in the late Silurian, a sea level drop resulted in a diagenetic sequence of meteoric phreatic alteration of marine cement and biotic components, which included precipitation of dolomite cements inter-grown within the meteoric phreatic calcite cement. This was post-dated by a coarse void filling calcite spar formed at burial temperatures of ~100°C (based on fluid inclusion analysis). Preliminary analyses of coexisting dolomite and calcite suggest that near-surface temperatures are preserved in dolomites despite having experienced elevated thermal diagenetic effects.. In contrast, co-existing early-formed calcites exhibit resetting of earth surface temperatures to elevated values. Δ47 measurements in dolomites yield temperatures around 30°C using the Guo et al., (2009) theoretical calibration. This contrasts with analyses of early (original) and late (hydrothermal) calcites, which record temperatures greater than ~80°C using the Δ47-calcite calibration of Dennis and Schrag (2010). These data support the hypothesis that dolomite can be a more resilient paleotemperature proxy relative to calcite in deep-time studies. Temperatures from dolomites compare reasonably with other late Silurian paleoclimate studies, and offer insight into regional-scale paleoclimate.

  16. Analysis of organophosphate flame retardants and plasticisers in water by isotope dilution gas chromatography-electron ionisation tandem mass spectrometry.

    PubMed

    Teo, Tiffany L L; McDonald, James A; Coleman, Heather M; Khan, Stuart J

    2015-10-01

    The widespread use of organophosphate flame retardants (PFRs) in commercial products have led to their increased presence in the environment. In this study, a rapid and reliable analytical method was developed for the analysis of five PFRs in water using gas chromatography tandem mass spectrometry (GC-MS/MS) with electron ionisation (EI) and a run time of 13 min. The PFRs investigated were tributyl phosphate (TBP), tris(2-chloroethyl) phosphate (TCEP), tris(1-chloro-2-propyl) phosphate (TCPP), tris(1,3-dichloro-2-propyl) phosphate (TDCP) and triphenyl phosphate (TPP). Solid phase extraction (SPE) was undertaken to extract and concentrate target analytes from aqueous matrices. All water samples were extracted from a volume of 500 mL. Isotopically labelled compounds were used to account for analytical variability and for accurate quantification by isotope dilution. Method recoveries for all compounds were above 80% in all tested water samples. Method detection limits for all target analytes ranged from 0.3 to 24 ng/L in ultrapure water, tap water, seawater, surface water, secondary effluent and swimming pool water. Validation of this method confirmed satisfactory method stability with less than 1% coefficients of variation, verifying that this approach produced good reproducibility. PMID:26078137

  17. Metal Oxide-Based Selective Enrichment Combined with Stable Isotope Labeling-Mass Spectrometry Analysis for Profiling of Ribose Conjugates.

    PubMed

    Chu, Jie-Mei; Qi, Chu-Bo; Huang, Yun-Qing; Jiang, Han-Peng; Hao, Yan-Hong; Yuan, Bi-Feng; Feng, Yu-Qi

    2015-07-21

    -SIL-LC-DNLS-MS strategy combines the selective enrichment, stable isotope labeling, and double neutral loss scan - MS analysis, which therefore can efficiently minimize false positive results, facilitate the relative quantification, and notably increase the numbers of identified ribose conjugates in biological fluids samples. Taken together, this study established a promising strategy for the effective profiling of urinary modified ribonucleosides, and simultaneous evaluation of the contents change of multiple modified ribonucleosides should provide more accurate and conclusive results for the use of urinary modified ribonucleosides as indicators of cancers.

  18. Kinetics of the reaction of the heaviest hydrogen atom with H2, the 4Heμ + H2 → 4HeμH + H reaction: experiments, accurate quantal calculations, and variational transition state theory, including kinetic isotope effects for a factor of 36.1 in isotopic mass.

    PubMed

    Fleming, Donald G; Arseneau, Donald J; Sukhorukov, Oleksandr; Brewer, Jess H; Mielke, Steven L; Truhlar, Donald G; Schatz, George C; Garrett, Bruce C; Peterson, Kirk A

    2011-11-14

    The neutral muonic helium atom (4)Heμ, in which one of the electrons of He is replaced by a negative muon, may be effectively regarded as the heaviest isotope of the hydrogen atom, with a mass of 4.115 amu. We report details of the first muon spin rotation (μSR) measurements of the chemical reaction rate constant of (4)Heμ with molecular hydrogen, (4)Heμ + H(2) → (4)HeμH + H, at temperatures of 295.5, 405, and 500 K, as well as a μSR measurement of the hyperfine coupling constant of muonic He at high pressures. The experimental rate constants, k(Heμ), are compared with the predictions of accurate quantum mechanical (QM) dynamics calculations carried out on a well converged Born-Huang (BH) potential energy surface, based on complete configuration interaction calculations and including a Born-Oppenheimer diagonal correction. At the two highest measured temperatures the agreement between the quantum theory and experiment is good to excellent, well within experimental uncertainties that include an estimate of possible systematic error, but at 295.5 K the quantum calculations for k(Heμ) are below the experimental value by 2.1 times the experimental uncertainty estimates. Possible reasons for this discrepancy are discussed. Variational transition state theory calculations with multidimensional tunneling have also been carried out for k(Heμ) on the BH surface, and they agree with the accurate QM rate constants to within 30% over a wider temperature range of 200-1000 K. Comparisons between theory and experiment are also presented for the rate constants for both the D + H(2) and Mu + H(2) reactions in a novel study of kinetic isotope effects for the H + H(2) reactions over a factor of 36.1 in isotopic mass of the atomic reactant.

  19. Development and validation of an universal interface for compound-specific stable isotope analysis of chlorine (37Cl/35Cl) by GC-high-temperature conversion (HTC)-MS/IRMS.

    PubMed

    Renpenning, Julian; Hitzfeld, Kristina L; Gilevska, Tetyana; Nijenhuis, Ivonne; Gehre, Matthias; Richnow, Hans-Hermann

    2015-03-01

    A universal application of compound-specific isotope analysis of chlorine was thus far limited by the availability of suitable analysis techniques. In this study, gas chromatography in combination with a high-temperature conversion interface (GC-HTC), converting organic chlorine in the presence of H2 to gaseous HCl, was coupled to a dual-detection system, combining an ion trap mass spectrometer (MS) and isotope-ratio mass spectrometer (IRMS). The combination of the MS/IRMS detection enabled a detailed characterization, optimization, and online monitoring of the high-temperature conversion process via ion trap MS as well as a simultaneous chlorine isotope analysis by the IRMS. Using GC-HTC-MS/IRMS, chlorine isotope analysis at optimized conversion conditions resulted in very accurate isotope values (δ(37)Cl(SMOC)) for measured reference material with known isotope composition, including chlorinated ethylene, chloromethane, hexachlorocyclohexane, and trichloroacetic acids methyl ester. Respective detection limits were determined to be <15 nmol Cl on column with achieved precision of <0.3‰.

  20. When other separation techniques fail: compound-specific carbon isotope ratio analysis of sulfonamide containing pharmaceuticals by high-temperature-liquid chromatography-isotope ratio mass spectrometry.

    PubMed

    Kujawinski, Dorothea M; Zhang, Lijun; Schmidt, Torsten C; Jochmann, Maik A

    2012-09-18

    Compound-specific isotope analysis (CISA) of nonvolatile analytes has been enabled by the introduction of the first commercial interface to hyphenate liquid chromatography with an isotope ratio mass spectrometer (LC-IRMS) in 2004, yet carbon isotope analysis of unpolar and moderately polar compounds is still a challenging task since only water as the eluent and no organic modifiers can be used to drive the separation in LC. The only way to increase the elution strength of aqueous eluents in reversed phase LC is the application of high temperatures to the mobile and stationary phases (HT-LC-IRMS). In this context we present the first method to determine carbon isotope ratios of pharmaceuticals that cannot be separated by already existing separation techniques for LC-IRMS, such as reversed phase chromatography at normal temperatures, ion-chromatography, and mixed mode chomatography. The pharmaceutical group of sulfonamides, which is generally mixed with trimethoprim in pharmaceutical products, has been chosen as probe compounds. Substance amounts as low as 0.3 μg are sufficient to perform a precise analysis. The successful applicability and reproducibility of this method is shown by the analysis of real pharmaceutical samples. The method provides the first tool to study the pharmaceutical authenticity as well as degradation and mobility of such substances in the environment by using the stable isotopic signature of these compounds.

  1. Compound-Specific Isotope Analysis of Nitroaromatic Contaminant Transformations by Nitroarene Dioxygenases

    NASA Astrophysics Data System (ADS)

    Pati, Sarah G.; Kohler, Hans-Peter E.; Hofstetter, Thomas B.

    2014-05-01

    Dioxygenation is an important biochemical reaction that often initiates the mineralization of recalcitrant organic contaminants such as nitroaromatic explosives, chlorinated benzenes, and polycyclic aromatic hydrocarbons. However, to assess the extent of dioxygenation in contaminated environments is difficult because of competing transformation processes and further reactions of the dioxygenation products. Compound-specific isotope analysis (CSIA) offers a new approach to reliably quantify biodegradation initiated by dioxygenation based on changes in stable isotope ratios of the pollutant. For CSIA it is essential to know the kinetic isotope effects (KIEs) pertinent to the dioxygenation mechanism of organic contaminants. Unfortunately, the range of KIEs of such reactions is poorly constrained although many dioxygenase enzymes with a broad substrate specificity have been reported. Dioxygenase enzymes usually exhibit complex reaction kinetics involving multiple substrates and substrate-specific binding modes which makes the determination of KIEs challenging. The goal of this study was to explore the magnitude and variability of 13C-, 2H-, and 15N-KIEs for the dioxygenation of one contaminant class, that is nitroaromatic contaminants (NACs). To this end, we investigated the C, H, and N isotope fractionation during the dioxygenation of nitrobenzene (NB), 2-nitrotoluene (2-NT), and 3-nitrotoluene (3-NT) by pure cultures, E. coli clones, cell extracts, and purified enzymes. From isotope fractionations measured in the substrates and reaction products, we determined dioxygenation KIEs for different combinations of the three substrates with nitrobenzene dioxygenase (NBDO) and 2-nitrotoluene dioxygenase (2NTDO). The 13C-, 2H-, and 15N-KIEs for the dioxygenation of NB by NBDO were consistent for all experimental systems considered (i.e., Comamonas sp. Strain JS765, E. coli clones, cell extracts of E. coli clones, and purified NBDO). This observation suggests that the isotope

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

    USGS Publications Warehouse

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

    2015-01-01

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

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

    PubMed Central

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

    2015-01-01

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

  4. Enhanced understanding of ectoparasite-host trophic linkages on coral reefs through stable isotope analysis.

    PubMed

    Demopoulos, Amanda W J; Sikkel, Paul C

    2015-04-01

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

  5. Effects of nitrate and water on the oxygen isotopic analysis of barium sulfate precipitated from solution

    USGS Publications Warehouse

    Hannon, Janet E.; Bohlke, Johnkarl F.; Mroczkowski, Stanley J.

    2008-01-01

    BaSO4 precipitated from mixed salt solutions by common techniques for SO isotopic analysis may contain quantities of H2O and NOthat introduce errors in O isotope measurements. Experiments with synthetic solutions indicate that δ18O values of CO produced by decomposition of precipitated BaSO4 in a carbon reactor may be either too low or too high, depending on the relative concentrations of SO and NO and the δ18O values of the H2O, NO, and SO. Typical δ18O errors are of the order of 0.5 to 1‰ in many sample types, and can be larger in samples containing atmospheric NO, which can cause similar errors in δ17O and Δ17O. These errors can be reduced by (1) ion chromatographic separation of SO from NO, (2) increasing the salinity of the solutions before precipitating BaSO4 to minimize incorporation of H2O, (3) heating BaSO4 under vacuum to remove H2O, (4) preparing isotopic reference materials as aqueous samples to mimic the conditions of the samples, and (5) adjusting measured δ18O values based on amounts and isotopic compositions of coexisting H2O and NO. These procedures are demonstrated for SO isotopic reference materials, synthetic solutions with isotopically known reagents, atmospheric deposition from Shenandoah National Park, Virginia, USA, and sulfate salt deposits from the Atacama Desert, Chile, and Mojave Desert, California, USA. These results have implications for the calibration and use of O isotope data in studies of SOsources and reaction mechanisms.

  6. Isotopic Dilution Analysis and Secular Equilibrium Study: Two Complementary Radiochemistry Experiments.

    ERIC Educational Resources Information Center

    Williams, Kathryn R.; Lipford, Levin C.

    1985-01-01

    Describes a complementary pair of radiochemistry experiments for instruction of isotopic dilution analysis and secular equilibrium. Both experiments use the readily available cesium-137 nuclide and the simple precipitation technique for cesium with the tetraphenylborate anion. Procedures used and typical results obtained are provided and…

  7. Analysis of tarnished plant bug movement using carbon and nitrogen isotopes

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Tarnished plant bug, Lygus lineolaris (Palisot de Beauvois), is the primary pest of cotton across the Midsouth of the United States. Movement into cotton fields occurs during the summer from other host plants, both cultivated and wild. Stable isotope analysis (SIA) has been used in other studies to ...

  8. Mucus: A new tissue fraction for rapid determination of fish diet switching using stable isotope analysis

    EPA Science Inventory

    Stable isotope analysis of diet switching by fishes often is hampered by slow turnover rates of the tissues analyzed (usually muscle or fins). We examined epidermal mucus as a potentially faster turnover “tissue” that might provide a more rapid assessment of diet switching. In a ...

  9. Mucus: a new tissue fraction for rapid determination of fish diet switching using stable isotope analysis.

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Stable isotope analysis of diet switching by fishes is often hampered by slow turnover rates of the tissues analyzed (usually muscle or fins). We examined epidermal mucus as a potentially faster turnover “tissue” that might provide a more rapid assessment of diet switching. In a controlled hatchery...

  10. Grazing food web view from compound-specific stable isotope analysis of amino acids

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Knowledge of the trophic position (TP) of organisms in food webs allows ecologists to track energy flow and trophic linkages among organisms in complex networks of ecosystems. Compound-specific stable isotope analysis (CSIA) of amino acids has been employed as a relatively new method with the high p...

  11. Linking ramped pyrolysis isotope data to oil content through PAH analysis

    NASA Astrophysics Data System (ADS)

    Pendergraft, Matthew A.; Dincer, Zeynep; Sericano, José L.; Wade, Terry L.; Kolasinski, Joanna; Rosenheim, Brad E.

    2013-12-01

    Ramped pyrolysis isotope (13C and 14C) analysis coupled with polycyclic aromatic hydrocarbon (PAH) analysis demonstrates the utility of ramped pyrolysis in screening for oil content in sediments. Here, sediments from Barataria Bay, Louisiana, USA that were contaminated by oil from the 2010 BP Deepwater Horizon spill display relationships between oil contamination, pyrolysis profiles, and isotopic composition. Sediment samples with low PAH concentrations are thermochemically stable until higher temperatures, while samples containing high concentrations of PAHs pyrolyze at low temperatures. High PAH samples are also depleted in radiocarbon (14C), especially in the fractions that pyrolyze at low temperatures. This lack of radiocarbon in low temperature pyrolyzates is indicative of thermochemically unstable, 14C-free oil content. This study presents a proof of concept that oil contamination can be identified by changes in thermochemical stability in organic material and corroborated by isotope analysis of individual pyrolyzates, thereby providing a basis for application of ramped pyrolysis isotope analysis to samples deposited in different environments for different lengths of time.

  12. Chemical Imaging and Stable Isotope Analysis of Atmospheric Particles by NanoSIMS (Invited)

    NASA Astrophysics Data System (ADS)

    Sinha, B.; Harris, E. J.; Pöhlker, C.; Wiedemann, K. T.; van Pinxteren, D.; Tilgner, A.; Fomba, K. W.; Schneider, J.; Roth, A.; Gnauk, T.; Fahlbusch, B.; Mertes, S.; Lee, T.; Collett, J. L.; Shiraiwa, M.; Gunthe, S. S.; Smith, M.; Artaxo, P. P.; Gilles, M.; Kilcoyne, A. L.; Moffet, R.; Weigand, M.; Martin, S. T.; Poeschl, U.; Andreae, M. O.; Hoppe, P.; Herrmann, H.; Borrmann, S.

    2013-12-01

    Chemical imaging analysis of the internal distribution of chemical compounds by a combination of SEM-EDX, and NanoSIMS allows investigating the physico-chemical properties and isotopic composition of individual aerosol particles. Stable sulphur isotope analysis provides insight into the sources, sinks and oxidation pathways of SO2 in the environment. Oxidation by OH radicals, O3 and H2O2 enriches the heavier isotope in the product sulphate, whereas oxidation by transition metal ions (TMI), hypohalites and hypohalous acids depletes the heavier isotope in the product sulphate. The isotope fractionation during SO2 oxidation by stabilized Criegee Intermediate radicals is unknown. We studied the relationship between aerosol chemical composition and predominant sulphate formation pathways in continental clouds in Central Europe and during the wet season in the Amazon rain forest. Sulphate formation in continental clouds in Central Europe was studied during HCCT-2010, a lagrangian-type field experiment, during which an orographic cloud was used as a natural flow-through reactor to study in-cloud aerosol processing (Harris et al. 2013). Sulphur isotopic compositions in SO2 and H2SO4 gas and particulate sulphate were measured and changes in the sulphur isotope composition of SO2 between the upwind and downwind measurement sites were used to determine the dominant SO2 chemical removal process occurring in the cloud. Changes in the isotopic composition of particulate sulphate revealed that transition metal catalysis pathway was the dominant SO2 oxidation pathway. This reaction occurred primarily on coarse mineral dust particles. Thus, sulphate produced due to in-cloud SO2 oxidation is removed relatively quickly from the atmosphere and has a minor climatic effect. The aerosol samples from the Amazonian rainforest, a pristine tropical environment, were collected during the rainy season. The samples were found to be dominated by SOA particles in the fine mode and primary

  13. INCA: a computational platform for isotopically non-stationary metabolic flux analysis

    PubMed Central

    2014-01-01

    Summary: 13C flux analysis studies have become an essential component of metabolic engineering research. The scope of these studies has gradually expanded to include both isotopically steady-state and transient labeling experiments, the latter of which are uniquely applicable to photosynthetic organisms and slow-to-label mammalian cell cultures. Isotopomer network compartmental analysis (INCA) is the first publicly available software package that can perform both steady-state metabolic flux analysis and isotopically non-stationary metabolic flux analysis. The software provides a framework for comprehensive analysis of metabolic networks using mass balances and elementary metabolite unit balances. The generation of balance equations and their computational solution is completely automated and can be performed on networks of arbitrary complexity. Availability and implementation: MATLAB p-code files are freely available for non-commercial use and can be downloaded at http://mfa.vueinnovations.com. Commercial licenses are also available. Contact: j.d.young@vanderbilt.edu PMID:24413674

  14. Oxygen isotope analysis of fossil organic matter by secondary ion mass spectrometry

    NASA Astrophysics Data System (ADS)

    Tartèse, Romain; Chaussidon, Marc; Gurenko, Andrey; Delarue, Frédéric; Robert, François

    2016-06-01

    We have developed an analytical procedure for the measurement of oxygen isotope composition of fossil organic matter by secondary ion mass spectrometry (SIMS) at the sub-per mill level, with a spatial resolution of 20-30 μm. The oxygen isotope composition of coal and kerogen samples determined by SIMS are on average consistent with the bulk oxygen isotope compositions determined by temperature conversion elemental analysis - isotope ratio mass spectrometry (TC/EA-IRMS), but display large spreads of δ18O of ∼5-10‰, attributed to mixing of remnants of organic compounds with distinct δ18O signatures. Most of the δ18O values obtained on two kerogen residues extracted from the Eocene Clarno and Early Devonian Rhynie continental chert samples and on two immature coal samples range between ∼10‰ and ∼25‰. Based on the average δ18O values of these samples, and on the O isotope composition of water processed by plants that now constitute the Eocene Clarno kerogen, we estimated δ18Owater values ranging between around -11‰ and -1‰, which overall correspond well within the range of O isotope compositions for present-day continental waters. SIMS analyses of cyanobacteria-derived organic matter from the Silurian Zdanow chert sample yielded δ18O values in the range 12-20‰. Based on the O isotope composition measured on recent cyanobacteria from the hypersaline Lake Natron (Tanzania), and on the O isotope composition of the lake waters in which they lived, we propose that δ18O values of cyanobacteria remnants are enriched by about ∼18 ± 2‰ to 22 ± 2‰ relative to coeval waters. This relationship suggests that deep ocean waters in which the Zdanow cyanobacteria lived during Early Silurian times were characterised by δ18O values of around -5 ± 4‰. This study, establishing the feasibility of micro-analysis of Phanerozoic fossil organic matter samples by SIMS, opens the way for future investigations of kerogens preserved in Archean cherts and of the

  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. Analysis of gas centrifuge cascade for separation of multicomponent isotopes and optimal feed position

    SciTech Connect

    Chuntong Ying; Hongjiang Wu; Mingsheng Zhou; Yuguang Nie; Guangjun Liu

    1997-10-01

    Analysis of the concentration distribution in a gas centrifuge cascade for separation of multicomponent isotope mixtures is different from that in a cascade for separation of two-component mixtures. This paper presents the governing equations for a multicomponent isotope separation cascade. Numerically predicted separation factors for the gas centrifuge cascade agree well with the experimental data. A theoretical optimal feed position is derived for a short square cascade for a two-component mixture in a close-separation case. The optimal feed position for a gas centrifuge cascade for separation of multicomponent mixture is discussed.

  17. Relativistic astrophysics. [design analysis and performance tests of Cerenkov counters for detection of iron isotopes

    NASA Technical Reports Server (NTRS)

    Price, P. B.

    1976-01-01

    The design, experimental testing, and calibration (error analysis) of a high resolution Cerenkov-scintillation detector is presented. The detector is capable of detecting iron isotopes and heavy ions of cosmic rays, and of performing direct measurements of individual neighboring isotopes at charge resolution 26. It utilizes Lexan (trademark) sheets, and has been used in flight packages of balloons and on the Skylab. The detector will be able to provide more information on violet astrophysical processes, such as thermonuclear reactions on neutron stars. Ground support and display equipment which are to be used in conjunction with the detector are also discussed.

  18. Uranium Isotopic and Quantitative Analysis Using a Mechanically-Cooled HPGe Detector

    SciTech Connect

    Solodov, Alexander A

    2008-01-01

    A new, portable high-resolution spectroscopy system based on a high-purity germanium detector cooled with a miniature Stirling-cycle cooler, ORTEC trans-SPEC, has recently become commercially available. The use of a long-life mechanical cooling system eliminates the need for liquid nitrogen. The purpose of this study was to determine the applicability of this new instrument for isotopic and quantitative analyses of uranium samples. The results of the performance of the trans-SPEC with the combination of PC-FRAM and ISOTOPIC software packages are described in this paper. An optimal set of analysis parameters for uranium measurements is proposed.

  19. Evidence for a possible dietary effect on the isotopic composition of Zn in blood via isotopic analysis of food products by multi-collector ICP-mass spectrometry.

    PubMed

    Costas-Rodríguez, Marta; Van Heghe, Lana; Vanhaecke, Frank

    2014-01-01

    In this work, the hypothesis of a possible dietary effect on the isotopic composition of Zn in blood from populations with different feeding habits, i.e. lacto-ovo vegetarians and omnivores, was investigated through isotopic analysis of Zn in common food products by multi-collector ICP - mass spectrometry (MC-ICP-MS). Several certified reference materials (CRMs) were also included in the sample set for comparison purposes. For these CRMs, the isotopic composition of Zn is expressed as δ-values, calculated with respect to both IRMM-3702 and JMC-ZnLyon, as isotopic standards. The range of δ(66)Zn values observed in food products was approximately 1.9‰. In general, vegetables, cereals and derived products showed an enrichment of the heavier Zn isotopes, whereas a depletion was observed in products of animal origin (meat, fish, egg and semi-skimmed milk), relative to human blood samples. Mussel, however, showed a significant enrichment of the heavier isotopes, which is hypothetically attributed to its accumulation behaviour. Thus, the lower δ(66)Zn values found in food products of animal origin appear to be reflected in the lower δ(66)Zn value observed in blood from an omnivorous population compared to that for a vegetarian population.

  20. Compound Specific Isotope Analysis of Fatty Acids in Southern African Aerosols

    NASA Astrophysics Data System (ADS)

    Billmark, K. A.; Macko, S. A.; Swap, R. J.

    2003-12-01

    This study, conducted as a part of the Southern African Regional Science Initiative (SAFARI 2000), applied compound specific isotope analysis to describe aerosols at source regions and rural locations. Stable carbon isotopic compositions of individual fatty acids were determined for aerosol samples collected at four sites throughout southern Africa. Mongu, Zambia and Skukuza, South Africa were chosen for their location within intense seasonal Miombo woodland savanna and bushveld savanna biomass burning source regions, respectively. Urban aerosols were collected at Johannesburg, South Africa and rural samples were collected at Sua Pan, Botswana. Fatty acid isotopic compositions varied temporally. Urban aerosols showed significant isotopic enrichment of selected short chain fatty acids (C < 20) compared to aerosols produced during biomass combustion. Sua Pan short chain fatty acid signatures were significantly different from the other non-urban sites, which suggests that sources other than biomass combustion products, such as organic eolian material, impact the Sua Pan aerosol profile. However, a high degree of correlation between Sua Pan and Skukuza long chain fatty acid δ 13C values confirm atmospheric linkages between the two areas and that isotopic signatures of combusted fatty acids are unaltered during atmospheric transport highlighting their potential for use as a conservative tracer.

  1. Collection of NO and NO2 for isotopic analysis of NO(x) emissions.

    PubMed

    Fibiger, Dorothy L; Hastings, Meredith G; Lew, Audrey F; Peltier, Richard E

    2014-12-16

    There have been several measurements made of the nitrogen isotopic composition of gaseous NOx (NOx = NO + NO2) from various emission sources, utilizing a wide variety of methods to collect the NOx in solution as nitrate or nitrite. However, previous collection techniques have not been verified for complete or efficient capture of NOx such that the isotopic composition of NOx remains unaltered during collection. Here, we present a method of collecting NOx (NO + NO2) in solution as nitrate to evaluate the nitrogen isotopic composition of the NOx (δ(15)N-NOx). Using a 0.25 M KMnO4 and 0.5 M NaOH solution, quantitative NOx collection was achieved under a variety of conditions in laboratory and field settings, allowing for isotopic analysis without correcting for fractionations. The uncertainty across the entire analytic procedure is ±1.5‰ (1σ). With this method, a more robust inventory of NOx source isotopic composition is possible, which has implications for studies of air quality and acid deposition. PMID:25415365

  2. Linking cases of illegal shootings of the endangered California condor using stable lead isotope analysis.

    PubMed

    Finkelstein, Myra E; Kuspa, Zeka E; Welch, Alacia; Eng, Curtis; Clark, Michael; Burnett, Joseph; Smith, Donald R

    2014-10-01

    Lead poisoning is preventing the recovery of the critically endangered California condor (Gymnogyps californianus) and lead isotope analyses have demonstrated that ingestion of spent lead ammunition is the principal source of lead poisoning in condors. Over an 8 month period in 2009, three lead-poisoned condors were independently presented with birdshot embedded in their tissues, evidencing they had been shot. No information connecting these illegal shooting events existed and the timing of the shooting(s) was unknown. Using lead concentration and stable lead isotope analyses of feathers, blood, and recovered birdshot, we observed that: i) lead isotope ratios of embedded shot from all three birds were measurably indistinguishable from each other, suggesting a common source; ii) lead exposure histories re-constructed from feather analysis suggested that the shooting(s) occurred within the same timeframe; and iii) two of the three condors were lead poisoned from a lead source isotopically indistinguishable from the embedded birdshot, implicating ingestion of this type of birdshot as the source of poisoning. One of the condors was subsequently lead poisoned the following year from ingestion of a lead buckshot (blood lead 556 µg/dL), illustrating that ingested shot possess a substantially greater lead poisoning risk compared to embedded shot retained in tissue (blood lead ~20 µg/dL). To our knowledge, this is the first study to use lead isotopes as a tool to retrospectively link wildlife shooting events.

  3. Stable Isotope Analysis Reveals Detrital Resource Base Sources of the Tree Hole Mosquito, Aedes triseriatus

    PubMed Central

    Kaufman, Michael G.; Pelz-Stelinski, Kirsten S.; Yee, Donald A.; Juliano, Steven A.; Ostrom, Peggy H.; Walker, Edward D.

    2010-01-01

    1. Detritus that forms the basis for mosquito production in tree hole ecosystems can vary in type and timing of input. We investigated the contributions of plant- and animal-derived detritus to the biomass of Aedes triseriatus (Say) pupae and adults by using stable isotope (15N and 13C) techniques in lab experiments and field collections. 2. Lab-reared mosquito isotope values reflected their detrital resource base, providing a clear distinction between mosquitoes reared on plant or animal detritus. 3. Isotope values from field-collected pupae were intermediate between what would be expected if a single (either plant or animal) detrital source dominated the resource base. However, mosquito isotope values clustered most closely with plant-derived values, and a mixed feeding model analysis indicated tree floral parts contributed approximately 80% of mosquito biomass. The mixed model also indicated that animal detritus contributed approximately 30% of mosquito tissue nitrogen. 4. Pupae collected later in the season generally had isotope values that were consistent with an increased contribution from animal detritus, suggesting this resource became more nutritionally important for mosquitoes as plant inputs declined over the summer. PMID:21132121

  4. Linking cases of illegal shootings of the endangered California condor using stable lead isotope analysis.

    PubMed

    Finkelstein, Myra E; Kuspa, Zeka E; Welch, Alacia; Eng, Curtis; Clark, Michael; Burnett, Joseph; Smith, Donald R

    2014-10-01

    Lead poisoning is preventing the recovery of the critically endangered California condor (Gymnogyps californianus) and lead isotope analyses have demonstrated that ingestion of spent lead ammunition is the principal source of lead poisoning in condors. Over an 8 month period in 2009, three lead-poisoned condors were independently presented with birdshot embedded in their tissues, evidencing they had been shot. No information connecting these illegal shooting events existed and the timing of the shooting(s) was unknown. Using lead concentration and stable lead isotope analyses of feathers, blood, and recovered birdshot, we observed that: i) lead isotope ratios of embedded shot from all three birds were measurably indistinguishable from each other, suggesting a common source; ii) lead exposure histories re-constructed from feather analysis suggested that the shooting(s) occurred within the same timeframe; and iii) two of the three condors were lead poisoned from a lead source isotopically indistinguishable from the embedded birdshot, implicating ingestion of this type of birdshot as the source of poisoning. One of the condors was subsequently lead poisoned the following year from ingestion of a lead buckshot (blood lead 556 µg/dL), illustrating that ingested shot possess a substantially greater lead poisoning risk compared to embedded shot retained in tissue (blood lead ~20 µg/dL). To our knowledge, this is the first study to use lead isotopes as a tool to retrospectively link wildlife shooting events. PMID:25173094

  5. Quantitative, Time-Resolved Proteomic Analysis by Combining Bioorthogonal Noncanonical Amino Acid Tagging and Pulsed Stable Isotope Labeling by Amino Acids in Cell Culture*

    PubMed Central

    Bagert, John D.; Xie, Yushu J.; Sweredoski, Michael J.; Qi, Yutao; Hess, Sonja; Schuman, Erin M.; Tirrell, David A.

    2014-01-01

    An approach to proteomic analysis that combines bioorthogonal noncanonical amino acid tagging (BONCAT) and pulsed stable isotope labeling with amino acids in cell culture (pSILAC) provides accurate quantitative information about rates of cellular protein synthesis on time scales of minutes. The method is capable of quantifying 1400 proteins produced by HeLa cells during a 30 min interval, a time scale that is inaccessible to isotope labeling techniques alone. Potential artifacts in protein quantification can be reduced to insignificant levels by limiting the extent of noncanonical amino acid tagging. We find no evidence for artifacts in protein identification in experiments that combine the BONCAT and pSILAC methods. PMID:24563536

  6. Stable isotope analysis of plant-derived nitrate - novel method for discrimination between organically and conventionally grown vegetables.

    PubMed

    Mihailova, A; Pedentchouk, N; Kelly, S D

    2014-07-01

    The lack of reliable markers for the discrimination between organic and conventional products makes the organic food market susceptible to attempted fraud. Robust analytical methodologies for organic food authentication are urgently needed. In this study a new approach, compound-specific nitrogen and oxygen isotope analysis of plant-derived nitrate, has been applied alongside bulk nitrogen isotope analysis for discrimination between organically and conventionally greenhouse-grown lettuce and retail potatoes and tomatoes. The method revealed significant differences between conventional and organic fertilisation. An intra-plant isotopic variation as well as significant impact of the fertiliser application rate on the nitrogen and oxygen isotope values of plant-derived nitrate has been observed. Nitrogen and oxygen isotope analysis of nitrate has a potential for differentiation between organic and conventional crops. Further analysis is needed to improve our understanding of the scope of application and robustness of this compound-specific approach. PMID:24518338

  7. Stable isotope analysis of plant-derived nitrate - novel method for discrimination between organically and conventionally grown vegetables.

    PubMed

    Mihailova, A; Pedentchouk, N; Kelly, S D

    2014-07-01

    The lack of reliable markers for the discrimination between organic and conventional products makes the organic food market susceptible to attempted fraud. Robust analytical methodologies for organic food authentication are urgently needed. In this study a new approach, compound-specific nitrogen and oxygen isotope analysis of plant-derived nitrate, has been applied alongside bulk nitrogen isotope analysis for discrimination between organically and conventionally greenhouse-grown lettuce and retail potatoes and tomatoes. The method revealed significant differences between conventional and organic fertilisation. An intra-plant isotopic variation as well as significant impact of the fertiliser application rate on the nitrogen and oxygen isotope values of plant-derived nitrate has been observed. Nitrogen and oxygen isotope analysis of nitrate has a potential for differentiation between organic and conventional crops. Further analysis is needed to improve our understanding of the scope of application and robustness of this compound-specific approach.

  8. Understanding N2O sources and sinks with laser based isotopic analysis

    NASA Astrophysics Data System (ADS)

    Mohn, J.

    2015-12-01

    Nitrous oxide (N2O) is a potent greenhouse gas and the strongest stratospheric ozone-destroying substance released in the 21st century. Main N2O emissions are linked to different microbial pathways, therefore sources are disperse and highly variable, complicating their interpretation. Isotopic measurements have great potential to distinguish between individual source and sink processes. Developments in laser spectroscopy allow both the intramolecular distribution of 15N substitutions (15N14N16O versus 14N15N16O) and the oxygen isotopic composition of N2O to be measured in real-time, at high precision and in excellent compatibility to IRMS [1]. In a number of laboratory and pilot plant studies we investigated the isotopic signature of distinct microbial and abiotic N2O production and consumption pathways in soil and aqueous solution [e.g. 2-4]. Specific pathways were favoured by selection of the nitrogen substrates and process conditions and their isotopic signatures identified by real-time laser spectroscopic analysis. Results from our laboratory studies are in accordance with pure culture experiments and can therefore be applied to other ecosystems. High precision isotopic analysis at ambient N2O concentration is feasible by combining laser spectroscopy with automated preconcentration. Field deployment was demonstrated by real-time monitoring of the isotopic composition of N2O emissions above an intensively managed grassland in central Switzerland. The responses of the N2O isotopic signatures were analysed with respect to management events and climatic conditions [5]. In a follow-up project we combine real-time N2O isotopic analysis at a tall tower in central Switzerland with atmospheric transport simulations and a biogeochemical model of surface fluxes of N2O isotopomers. The working hypothesis is that this approach will allow us to quantify regional N2O sources, identify emission hot spots, and constrain source processes, which will significantly advance our

  9. In-situ chemical and isotopic analysis of a comet by Ptolemy

    NASA Astrophysics Data System (ADS)

    Morse, A. D.; Barber, S. J.; Leese, M. R.; Morgan, G. H.; Sheridan, S.; Wright, I. P.; Zarnecki, J. C.; Pillinger, C. T.

    2003-04-01

    Ptolemy is a Gas Chromatograph - Mass Spectrometer, one of the instruments on board the Rosetta Lander, intended to land on comet Wirtanen. Ptolemy is designed to measure the composition and isotope ratios of gases released from comet samples during pyrolysis or combustion. The total mass of the instrument is 4.6 kg and it fits into a space of 33 x 25 x 11 cm. Following touchdown on the comet nucleus, comet samples are obtained by the SD2 instrument, which drills a core sample and loads it into one of 26 ovens on a carousel. One of the ovens already contains a molecular sieve absorbent so that the comet "atmosphere" can also be sampled. The sample is then heated by the oven and the gases released are transferred to the Ptolemy instrument. Within Ptolemy, the raw sample gases can be chemically processed to convert them into molecules suitable for isotopic analysis. The processed sample mixture gas is injected into one of three GC columns to separate it into its constituent components before analysis by the mass spectrometer. An ion trap mass spectrometer has been used as this gives considerable reduction of mass, power and volume, compared to standard magnetic sector mass spectrometers normally used for isotopic analysis. Laboratory experiments have shown that an ion trap is capable of measuring carbon and nitrogen isotope ratios to a precision of +/- 20 per mil or better. We will present data from the Flight instrument plus results of ongoing characterisation studies using the identical Qualification Model.

  10. Fourier Transform Mass Spectrometry and Nuclear Magnetic Resonance Analysis for the Rapid and Accurate Characterization of Hexacosanoylceramide.

    PubMed

    Ross, Charles W; Simonsick, William J; Bogusky, Michael J; Celikay, Recep W; Guare, James P; Newton, Randall C

    2016-06-28

    Ceramides are a central unit of all sphingolipids which have been identified as sites of biological recognition on cellular membranes mediating cell growth and differentiation. Several glycosphingolipids have been isolated, displaying immunomodulatory and anti-tumor activities. These molecules have generated considerable interest as potential vaccine adjuvants in humans. Accurate analyses of these and related sphingosine analogues are important for the characterization of structure, biological function, and metabolism. We report the complementary use of direct laser desorption ionization (DLDI), sheath flow electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) and high-field nuclear magnetic resonance (NMR) analysis for the rapid, accurate identification of hexacosanoylceramide and starting materials. DLDI does not require stringent sample preparation and yields representative ions. Sheath-flow ESI yields ions of the product and byproducts and was significantly better than monospray ESI due to improved compound solubility. Negative ion sheath flow ESI provided data of starting materials and products all in one acquisition as hexacosanoic acid does not ionize efficiently when ceramides are present. NMR provided characterization of these lipid molecules complementing the results obtained from MS analyses. NMR data was able to differentiate straight chain versus branched chain alkyl groups not easily obtained from mass spectrometry.

  11. An accurate retrieval of leaf water content from mid to thermal infrared spectra using continuous wavelet analysis.

    PubMed

    Ullah, Saleem; Skidmore, Andrew K; Naeem, Mohammad; Schlerf, Martin

    2012-10-15

    Leaf water content determines plant health, vitality, photosynthetic efficiency and is an important indicator of drought assessment. The retrieval of leaf water content from the visible to shortwave infrared spectra is well known. Here for the first time, we estimated leaf water content from the mid to thermal infrared (2.5-14.0 μm) spectra, based on continuous wavelet analysis. The dataset comprised 394 spectra from nine plant species, with different water contents achieved through progressive drying. To identify the spectral feature most sensitive to the variations in leaf water content, first the Directional Hemispherical Reflectance (DHR) spectra were transformed into a wavelet power scalogram, and then linear relations were established between the wavelet power scalogram and leaf water content. The six individual wavelet features identified in the mid infrared yielded high correlations with leaf water content (R(2)=0.86 maximum, 0.83 minimum), as well as low RMSE (minimum 8.56%, maximum 9.27%). The combination of four wavelet features produced the most accurate model (R(2)=0.88, RMSE=8.00%). The models were consistent in terms of accuracy estimation for both calibration and validation datasets, indicating that leaf water content can be accurately retrieved from the mid to thermal infrared domain of the electromagnetic radiation.

  12. Fourier Transform Mass Spectrometry and Nuclear Magnetic Resonance Analysis for the Rapid and Accurate Characterization of Hexacosanoylceramide

    PubMed Central

    Ross, Charles W.; Simonsick, William J.; Bogusky, Michael J.; Celikay, Recep W.; Guare, James P.; Newton, Randall C.

    2016-01-01

    Ceramides are a central unit of all sphingolipids which have been identified as sites of biological recognition on cellular membranes mediating cell growth and differentiation. Several glycosphingolipids have been isolated, displaying immunomodulatory and anti-tumor activities. These molecules have generated considerable interest as potential vaccine adjuvants in humans. Accurate analyses of these and related sphingosine analogues are important for the characterization of structure, biological function, and metabolism. We report the complementary use of direct laser desorption ionization (DLDI), sheath flow electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) and high-field nuclear magnetic resonance (NMR) analysis for the rapid, accurate identification of hexacosanoylceramide and starting materials. DLDI does not require stringent sample preparation and yields representative ions. Sheath-flow ESI yields ions of the product and byproducts and was significantly better than monospray ESI due to improved compound solubility. Negative ion sheath flow ESI provided data of starting materials and products all in one acquisition as hexacosanoic acid does not ionize efficiently when ceramides are present. NMR provided characterization of these lipid molecules complementing the results obtained from MS analyses. NMR data was able to differentiate straight chain versus branched chain alkyl groups not easily obtained from mass spectrometry. PMID:27367671

  13. Determination of geographic provenance of cotton fibres using multi-isotope profiles and multivariate statistical analysis

    NASA Astrophysics Data System (ADS)

    Daeid, N. Nic; Meier-Augenstein, W.; Kemp, H. F.

    2012-04-01

    The analysis of cotton fibres can be particularly challenging within a forensic science context where discrimination of one fibre from another is of importance. Normally cotton fibre analysis examines the morphological structure of the recovered material and compares this with that of a known fibre from a particular source of interest. However, the conventional microscopic and chemical analysis of fibres and any associated dyes is generally unsuccessful because of the similar morphology of the fibres. Analysis of the dyes which may have been applied to the cotton fibre can also be undertaken though this can be difficult and unproductive in terms of discriminating one fibre from another. In the study presented here we have explored the potential for Isotope Ratio Mass Spectrometry (IRMS) to be utilised as an additional tool for cotton fibre analysis in an attempt to reveal further discriminatory information. This work has concentrated on un-dyed cotton fibres of known origin in order to expose the potential of the analytical technique. We report the results of a pilot study aimed at testing the hypothesis that multi-element stable isotope analysis of cotton fibres in conjunction with multivariate statistical analysis of the resulting isotopic abundance data using well established chemometric techniques permits sample provenancing based on the determination of where the cotton was grown and as such will facilitate sample discrimination. To date there is no recorded literature of this type of application of IRMS to cotton samples, which may be of forensic science relevance.

  14. A Simple and Accurate Analysis of Conductivity Loss in Millimeter-Wave Helical Slow-Wave Structures

    NASA Astrophysics Data System (ADS)

    Datta, S. K.; Kumar, Lalit; Basu, B. N.

    2009-04-01

    Electromagnetic field analysis of a helix slow-wave structure was carried out and a closed form expression was derived for the inductance per unit length of the transmission-line equivalent circuit of the structure, taking into account the actual helix tape dimensions and surface current on the helix over the actual metallic area of the tape. The expression of the inductance per unit length, thus obtained, was used for estimating the increment in the inductance per unit length caused due to penetration of the magnetic flux into the conducting surfaces following Wheeler’s incremental inductance rule, which was subsequently interpreted for the attenuation constant of the propagating structure. The analysis was computationally simple and accurate, and accrues the accuracy of 3D electromagnetic analysis by allowing the use of dispersion characteristics obtainable from any standard electromagnetic modeling. The approach was benchmarked against measurement for two practical structures, and excellent agreement was observed. The analysis was subsequently applied to demonstrate the effects of conductivity on the attenuation constant of a typical broadband millimeter-wave helical slow-wave structure with respect to helix materials and copper plating on the helix, surface finish of the helix, dielectric loading effect and effect of high temperature operation - a comparative study of various such aspects are covered.

  15. Frontiers of QC Laser spectroscopy for high precision isotope ratio analysis of greenhouse gases

    NASA Astrophysics Data System (ADS)

    Emmenegger, Lukas; Mohn, Joachim; Harris, Eliza; Eyer, Simon; Ibraim, Erkan; Tuzson, Béla

    2016-04-01

    An important milestone for laser spectroscopy was achieved when isotope ratios of greenhouse gases were reported at precision levels that allow addressing research questions in environmental sciences. Real-time data with high temporal resolution at moderate cost and instrument size make the optical approach highly attractive, complementary to the well-established isotope-ratio mass-spectrometry (IRMS) method. Especially appealing, in comparison to IRMS, is the inherent specificity to structural isomers having the same molecular mass. Direct absorption in the MIR in single or dual QCL configuration has proven highly reliable for the sta-ble isotopes of CO2, N2O and CH4. The longest time series of real-time measurements is currently available for δ13C and δ18O in CO2 at the high-alpine station Jung-fraujoch. At this well-equipped site, QCL based direct absorption spectroscopy (QCLAS) measurements are ongoing since 2008 1,2. Applications of QCLAS for N2O and CH4 stable isotopes are considerably more challenging because of the lower atmospheric mixing ratios, especially for the less abundant species, such as N218O and CH3D. For high precision (< 0.1 ‰) measurements in ambient air, QCLAS may be combined with a fully automated preconcentration unit yielding an up to 500 times concentration increase and the capability to separate the target gas from spectral interferants by se-quential desorption 3. Here, we review our recent developments on high precision isotope ratio analysis of greenhouse gases, with special focus on the isotopic species of N2O and CH4. Furthermore, we show environ-mental applications illustrating the highly valuable information that isotope ratios of atmospheric trace gases can carry. For example, the intramolecular distribution of 15N in N2O gives important information on the geochemical cycle of N2O4-6, while the analysis of δ13C and δ D in CH4 may be applied to disentangle microbial, fossil and landfill sources 7. 1 Sturm, P., Tuzson, B

  16. Evaluation of strontium isotope abundance ratios in combination with multi-elemental analysis as a possible tool to study the geographical origin of ciders.

    PubMed

    García-Ruiz, Silvia; Moldovan, Mariella; Fortunato, Giuseppino; Wunderli, Samuel; García Alonso, J Ignacio

    2007-05-01

    In order to evaluate alternative analytical methodologies to study the geographical origin of ciders, both multi-elemental analysis and Sr isotope abundance ratios in combination with multivariate statistical analysis were estimated in 67 samples from England, Switzerland, France and two Spanish regions (Asturias and the Basque Country). A methodology for the precise and accurate determination of the (87)Sr/(86)Sr isotope abundance ratio in ciders by multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) was developed. Major elements (Na, K, Ca and Mg) were measured by ICP-AES and minor and trace elements (Li, Be, B, Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Y, Mo, Cd, Sn, Sb, Cs, Ba, La, Ce, W, Tl, Pb, Bi, Th and U) were measured by ICP-MS using a collision cell instrument operated in multitune mode. An analysis of variance (ANOVA test) indicated that group means for B, Cr, Fe, Ni, Cu, Se, Cd, Cs, Ce, W, Pb, Bi and U did not show any significant differences at the 95% confidence level, so these elements were rejected for further statistical analysis. Another group of elements (Li, Be, Sc, Co, Ga, Y, Sn, Sb, La, Tl, Th) was removed from the data set because concentrations were close to the limits of detection for many samples. Therefore, the remaining elements (Na, Mg, Al, K, Ca, Ti, V, Mn, Zn, As, Rb, Sr, Mo, Ba) together with (87)Sr/(86)Sr isotope abundance ratio were considered for principal component analysis (PCA) and linear discriminant analysis (LDA). Finally, LDA was able to classify correctly 100% of cider samples coming from different Spanish regions, France, England and Switzerland when considering Na, Mg, Al, K, Ca, Ti, V, Mn, Zn, As, Rb, Sr, Mo, Ba and (87)Sr/(86)Sr isotope abundance ratio as original variables. PMID:17416223

  17. Coordinated Mineralogical and Isotopic Analysis of a Cosmic Symplectite Identified in a Stardust Terminal Particle

    NASA Technical Reports Server (NTRS)

    Nguyen, A. N.; Berger, E. L.; Nakamura-Messenger, K.; Messenger, S.

    2014-01-01

    Comet Wild-2 samples returned by the Stardust spacecraft contain a chemically diverse mixture of material, underscoring the complex nature of comets. Studies of entire Stardust aerogel tracks afford the opportunity to examine the fine-grained particle fragments distributed along the length of the track as well as the terminal particles. Previous TEM characterization of a terminal particle (TP) in track #147 revealed a symplectically intergrown iron sulfide and oxide assemblage. Mineralogically similar assemblages, known as cosmic symplectites (COS, formerly termed "new-PCP"), have only been identified in the primitive carbonaceous chondrite Acfer 094. Meteoritic COS have isotopically heavy O compositions (delta (sup 17), O-18 = 180per mille) that point to interactions with early solar system primordial water. In this study we report mineralogical and O isotopic measurements of the Wild-2 COS assemblage. Experimental: Track #147 is a "bulbous"-type track (4600 microns long) containing 7 terminal particles. The TPs were removed from the track, embedded in epoxy, and ultramicrotomed. A JEOL 2500SE 200 keV field-emission scanning-transmission electron microscope was used to obtain quantitative elemental maps and detailed mineralogical characterization. Following TEM analysis, two thin sections of TP4 (12 microns) were analyzed for O isotopes by raster ion imaging with the JSC NanoSIMS 50L. All three O isotopes were measured simultaneously using electron multipliers. San Carlos olivine grains were used as isotopic standards. Results and Discussion: The COS in the Wild-2 track #147 TP4 sample consists of symplectically intergrown pentlandite and nanocrystalline maghemite which coexists with high-Ca pyroxene with Na and Cr (kosmochlor component). This kosmochlor component could have a nebular origin and be precursors to type II chondrules in ordinary chondrites. Yet pentlandite is not a stable phase in the nebula. The COS in Acfer 094 also consists of pentlandite, but

  18. Investigation of low-abundant in vitro metabolites of stable isotope-labelled BAL4815 by accurate mass capillary-LC-ESI-qTof-MS and MS/MS.

    PubMed

    Wind, Mathias; Spickermann, Jochen; Schleimer, Michael; Donzelli, Massimiliano; Gebhardt, Klaus; Sturm-Haurany, Rima; Klauer, Dominique; Fullhardt, Pascal; Schmitt-Hoffmann, Anne

    2006-07-01

    The metabolic profile of BAL4815, an antifungal azole drug, was determined using in vitro rat hepatocyte incubations and subsequent analysis by capillary LC-qTof-MS and MS/MS including accurate mass determination. For the detection of the metabolites, a mixture of the drug and its deuterium-labelled analogue was used for incubations. Metabolic stability of BAL4815 was high in cultured rat hepatocytes. However, several low-abundant metabolites were detected by the use of capillary LC-qTof-MS and manual investigation of the data. The peak intensity of the most abundant metabolite was close to the limit of detection. Except for an apparent oxidation product, the masses of the other detected metabolites could not be assigned to a single and frequently occurring biotransformation. Accurate mass determination and possible elemental compositions suggested that metabolism occurred through a combination of glutathionylation and defluorination. This was verified using accurate mass MS/MS. The use of accurate mass measurements and the derived suggestions for the elemental compositions were essential to elucidate this atypical metabolic pathway. A mass accuracy better than 8 ppm could be achieved for most assigned MS and MS/MS signals with intensities less than 6 cps in the spectra.

  19. Isolation and derivatization of plasma taurine for stable isotope analysis by gas chromatography-mass spectrometry

    SciTech Connect

    Irving, C.S.; Klein, P.D.

    1980-09-01

    A method for the isolation and derivatization of plasma taurine is described that allows stable isotope determinations of taurine to be made by gas chromatography-mass spectrometry. The isolation procedure can be applied to 0.1 ml of plasma; the recovery of plasma taurine was 70 to 80%. For gc separation, taurine was converted to its dimethylaminomethylene methyl ester derivative which could not be detected by hydrogen flame ionization, but could be monitored readily by NH/sub 3/ chemical ionization mass spectrometry. The derivatization reaction occurred partially on-column and required optimization of injection conditions. Using stable isotope ratiometry multiple ion detection, (M + 2 + H)/sup +//(M + H)/sup +/ ion ratio of natural abundance taurine was determined with a standard deviation of less than +-0.07% of the ratio. The (1,2-/sup 13/C)taurine/taurine mole ratios of standard mixtures could be accurately determined to 0.001. This stable isotope gc-ms method is suitable for studying the plasma kinetics of (1,2-/sup 13/C)taurine in infants who are at risk with respect to taurine depletion.

  20. Simple, fast, and accurate methodology for quantitative analysis using Fourier transform infrared spectroscopy, with bio-hybrid fuel cell examples.

    PubMed

    Mackie, David M; Jahnke, Justin P; Benyamin, Marcus S; Sumner, James J

    2016-01-01

    The standard methodologies for quantitative analysis (QA) of mixtures using Fourier transform infrared (FTIR) instruments have evolved until they are now more complicated than necessary for many users' purposes. We present a simpler methodology, suitable for widespread adoption of FTIR QA as a standard laboratory technique across disciplines by occasional users.•Algorithm is straightforward and intuitive, yet it is also fast, accurate, and robust.•Relies on component spectra, minimization of errors, and local adaptive mesh refinement.•Tested successfully on real mixtures of up to nine components. We show that our methodology is robust to challenging experimental conditions such as similar substances, component percentages differing by three orders of magnitude, and imperfect (noisy) spectra. As examples, we analyze biological, chemical, and physical aspects of bio-hybrid fuel cells.

  1. Accurate Enumeration of Aspergillus brasiliensis in Hair Color and Mascara by Time-Lapse Shadow Image Analysis.

    PubMed

    Ogawa, Hiroyuki; Matsuoka, Hideaki; Saito, Mikako

    2015-01-01

    The growth of black mold (Aspergillus brasiliensis) in black-colored samples such as hair color and mascara was measured with an automatic count system based on time-lapse shadow image analysis (TSIA). A. brasiliensis suspended in a lecithin and polysorbate (LP) solution of each sample (hair color or mascara) was spread on a potato dextrose agar medium plate containing LP. The background image darkness of the agar plate could be adjusted to attain accurate colony counts. 95 colonies in hair color and 22 colonies in mascara could be automatically determined at 48 h. The accuracy of the colony counts could be confirmed from the timelapse image data. In contrast, conventional visual counting at a specified time could not determine the number of colonies or led to false colony counts.

  2. Simple, fast, and accurate methodology for quantitative analysis using Fourier transform infrared spectroscopy, with bio-hybrid fuel cell examples

    PubMed Central

    Mackie, David M.; Jahnke, Justin P.; Benyamin, Marcus S.; Sumner, James J.

    2016-01-01

    The standard methodologies for quantitative analysis (QA) of mixtures using Fourier transform infrared (FTIR) instruments have evolved until they are now more complicated than necessary for many users’ purposes. We present a simpler methodology, suitable for widespread adoption of FTIR QA as a standard laboratory technique across disciplines by occasional users.•Algorithm is straightforward and intuitive, yet it is also fast, accurate, and robust.•Relies on component spectra, minimization of errors, and local adaptive mesh refinement.•Tested successfully on real mixtures of up to nine components. We show that our methodology is robust to challenging experimental conditions such as similar substances, component percentages differing by three orders of magnitude, and imperfect (noisy) spectra. As examples, we analyze biological, chemical, and physical aspects of bio-hybrid fuel cells. PMID:26977411

  3. Development of high through-put Sr isotope analysis for monitoring reservoir integrity for CO{sub 2} storage.

    SciTech Connect

    Wall, Andy; Jain, Jinesh; Stewart, Brian; Capo, Rosemary; Hakala, Alexandra J.; Hammack, Richard; Guthrie, George

    2012-01-01

    Recent innovations in multi-collector ICP-mass spectrometry (MC-ICP-MS) have allowed for rapid and precise measurements of isotope ratios in geological samples. Naturally occurring Sr isotopes has the potential for use in Monitoring, Verification, and Accounting (MVA) associated with geologic CO2 storage. Sr isotopes can be useful for: Sensitive tracking of brine migration; Determining seal rock leakage; Studying fluid/rock reactions. We have optimized separation chemistry procedures that will allow operators to prepare samples for Sr isotope analysis off site using rapid, low cost methods.

  4. Documenting the diet in ancient human populations through stable isotope analysis of hair.

    PubMed

    Macko, S A; Engel, M H; Andrusevich, V; Lubec, G; O'Connell, T C; Hedges, R E

    1999-01-29

    Fundamental to the understanding of human history is the ability to make interpretations based on artefacts and other remains which are used to gather information about an ancient population. Sequestered in the organic matrices of these remains can be information, for example, concerning incidence of disease, genetic defects and diet. Stable isotopic compositions, especially those made on isolates of collagen from bones, have been used to help suggest principal dietary components. A significant problem in the use of collagen is its long-term stability, and the possibility of isotopic alteration during early diagenesis, or through contaminating condensation reactions. In this study, we suggest that a commonly overlooked material, human hair, may represent an ideal material to be used in addressing human diets of ancient civilizations. Through the analysis of the amino-acid composition of modern hair, as well as samples that were subjected to radiation (thus simulating ageing of the hair) and hair from humans that is up to 5200 years old, we have observed little in the way of chemical change. The principal amino acids observed in all of these samples are essentially identical in relative abundances and content. Dominating the compositions are serine, glutamic acid, threonine, glycine and leucine, respectively accounting for approximately 15%, 17%, 10%, 8% and 8% of the total hydrolysable amino acids. Even minor components (for example, alanine, valine, isoleucine) show similar constancy between the samples of different ages. This constancy clearly indicates minimal alteration of the amino-acid composition of the hair. Further, it would indicate that hair is well preserved and is amenable to isotopic analysis as a tool for distinguishing sources of nutrition. Based on this observation, we have isotopically characterized modern individuals for whom the diet has been documented. Both stable nitrogen and carbon isotope compositions were assessed, and together provide an

  5. Documenting the diet in ancient human populations through stable isotope analysis of hair.

    PubMed Central

    Macko, S A; Engel, M H; Andrusevich, V; Lubec, G; O'Connell, T C; Hedges, R E

    1999-01-01

    Fundamental to the understanding of human history is the ability to make interpretations based on artefacts and other remains which are used to gather information about an ancient population. Sequestered in the organic matrices of these remains can be information, for example, concerning incidence of disease, genetic defects and diet. Stable isotopic compositions, especially those made on isolates of collagen from bones, have been used to help suggest principal dietary components. A significant problem in the use of collagen is its long-term stability, and the possibility of isotopic alteration during early diagenesis, or through contaminating condensation reactions. In this study, we suggest that a commonly overlooked material, human hair, may represent an ideal material to be used in addressing human diets of ancient civilizations. Through the analysis of the amino-acid composition of modern hair, as well as samples that were subjected to radiation (thus simulating ageing of the hair) and hair from humans that is up to 5200 years old, we have observed little in the way of chemical change. The principal amino acids observed in all of these samples are essentially identical in relative abundances and content. Dominating the compositions are serine, glutamic acid, threonine, glycine and leucine, respectively accounting for approximately 15%, 17%, 10%, 8% and 8% of the total hydrolysable amino acids. Even minor components (for example, alanine, valine, isoleucine) show similar constancy between the samples of different ages. This constancy clearly indicates minimal alteration of the amino-acid composition of the hair. Further, it would indicate that hair is well preserved and is amenable to isotopic analysis as a tool for distinguishing sources of nutrition. Based on this observation, we have isotopically characterized modern individuals for whom the diet has been documented. Both stable nitrogen and carbon isotope compositions were assessed, and together provide an

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

    PubMed

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

    2016-01-15

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

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

    PubMed

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

    2016-01-15

    In forensic environmental investigations the main issue concerns the inference of the original source of the pollutant for determining the liable party. Isotope measurements in geochemistry, combined with complimentary techniques for contaminant identification, have contributed significantly to source determination at polluted sites. In this work we have determined the intramolecular (13)C profiles of several molecules well-known as pollutants. By giving additional analytical parameters, position-specific isotope analysis performed by isotope ratio monitoring by (13)C nuclear magnetic resonance (irm-(13)C NMR) spectrometry gives new information to help in answering the major question: what is the origin of the detected contaminant? We have shown that isotope profiling of the core of a molecule reveals both the raw materials and the process used in its manufacture. It also can reveal processes occurring between the contamination site 'source' and the sampling site. Thus, irm-(13)C NMR is shown to be a very good complement to compound-specific isotope analysis currently performed by mass spectrometry for assessing polluted sites involving substantial spills of pollutant. PMID:26592622

  8. Online analysis of chlorine stable isotopes in chlorinated ethylenes: an inter-laboratory study

    NASA Astrophysics Data System (ADS)

    Bernstein, Anat; Shouakar-Stash, Orfan; Hunkeler, Daniel; Sakaguchi-Söder, Kaori; Laskov, Christine; Aravena, Ramon; Elsner, Martin

    2010-05-01

    In the last decade, compound-specific stable isotopes analysis of groundwater pollutants became an important tool to identify different sources of the same pollutant and for tracking natural attenuating processes in the sub-surface. It has been shown that trends in the isotopic composition of the target compounds can shed light on in-situ processes that are otherwise difficult to track. Analytical methods of carbon, nitrogen and hydrogen were established and are by now frequently used for a variety of organic pollutants. Yet, the motivation of introducing analytical methods for new isotopes is emerging. This motivation is further enhanced, as advantages of using two or more stable isotopes for gaining better insight on degradation pathways are well accepted. One important element which demands the development of appropriate analytical methods is chlorine, which is found in various groups of organic pollutants, among them the chlorinated ethylenes. Chlorinated ethylenes are considered as high priority environmental pollutants, and the development of suitable chlorine isotope methods for this group of pollutants is highly desired. Ideally, stable isotope techniques should have the capability to determine the isotopic composition of and individual target compound in a non-pure mixture, without the requirement of a laborious off-line treatment. Indeed, in the last years two different concepts for on-line chlorine isotope analysis methods were introduced, by using either a standard quadrapole GC/MS (Sakaguchi-Söder et al., 2007) or by using a GC/IRMS (Shouakar-Stash et al., 2006). We present a comparison of the performances of two concepts, carried out in five different laboratories: Waterloo (GC/IRMS), Neuchâtel (GC/MS), Darmstadt (GC/MS), Tübingen (GC/MS) and Munich (GC/IRMS). This comparison was performed on pure trichloroethylene and dichloroethylene products of different manufactures, as well as trichloroethylene and dichloroethylene samples that were exposed to

  9. Development of routines for simultaneous in situ chemical composition and stable Si isotope ratio analysis by femtosecond laser ablation inductively coupled plasma mass spectrometry.

    PubMed

    Frick, Daniel A; Schuessler, Jan A; von Blanckenburg, Friedhelm

    2016-09-28

    Stable metal (e.g. Li, Mg, Ca, Fe, Cu, Zn, and Mo) and metalloid (B, Si, Ge) isotope ratio systems have emerged as geochemical tracers to fingerprint distinct physicochemical reactions. These systems are relevant to many Earth Science questions. The benefit of in situ microscale analysis using laser ablation (LA) over bulk sample analysis is to use the spatial context of different phases in the solid sample to disclose the processes that govern their chemical and isotopic compositions. However, there is a lack of in situ analytical routines to obtain a samples' stable isotope ratio together with its chemical composition. Here, we evaluate two novel analytical routines for the simultaneous determination of the chemical and Si stable isotope composition (δ(30)Si) on the micrometre scale in geological samples. In both routines, multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) is combined with femtosecond-LA, where stable isotope ratios are corrected for mass bias using standard-sample-bracketing with matrix-independent calibration. The first method is based on laser ablation split stream (LASS), where the laser aerosol is split and introduced simultaneously into both the MC-ICP-MS and a quadrupole ICP-MS. The second method is based on optical emission spectroscopy using direct observation of the MC-ICP-MS plasma (LA-MC-ICP-MS|OES). Both methods are evaluated using international geological reference materials. Accurate and precise Si isotope ratios were obtained with an uncertainty typically better than 0.23‰, 2SD, δ(30)Si. With both methods major element concentrations (e.g., Na, Al, Si, Mg, Ca) can be simultaneously determined. However, LASS-ICP-MS is superior over LA-MC-ICP-MS|OES, which is limited by its lower sensitivity. Moreover, LASS-ICP-MS offers trace element analysis down to the μg g(-1)-range for more than 28 elements due to lower limits of detection, and with typical uncertainties better than 15%. For in situ simultaneous

  10. Development of routines for simultaneous in situ chemical composition and stable Si isotope ratio analysis by femtosecond laser ablation inductively coupled plasma mass spectrometry.

    PubMed

    Frick, Daniel A; Schuessler, Jan A; von Blanckenburg, Friedhelm

    2016-09-28

    Stable metal (e.g. Li, Mg, Ca, Fe, Cu, Zn, and Mo) and metalloid (B, Si, Ge) isotope ratio systems have emerged as geochemical tracers to fingerprint distinct physicochemical reactions. These systems are relevant to many Earth Science questions. The benefit of in situ microscale analysis using laser ablation (LA) over bulk sample analysis is to use the spatial context of different phases in the solid sample to disclose the processes that govern their chemical and isotopic compositions. However, there is a lack of in situ analytical routines to obtain a samples' stable isotope ratio together with its chemical composition. Here, we evaluate two novel analytical routines for the simultaneous determination of the chemical and Si stable isotope composition (δ(30)Si) on the micrometre scale in geological samples. In both routines, multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) is combined with femtosecond-LA, where stable isotope ratios are corrected for mass bias using standard-sample-bracketing with matrix-independent calibration. The first method is based on laser ablation split stream (LASS), where the laser aerosol is split and introduced simultaneously into both the MC-ICP-MS and a quadrupole ICP-MS. The second method is based on optical emission spectroscopy using direct observation of the MC-ICP-MS plasma (LA-MC-ICP-MS|OES). Both methods are evaluated using international geological reference materials. Accurate and precise Si isotope ratios were obtained with an uncertainty typically better than 0.23‰, 2SD, δ(30)Si. With both methods major element concentrations (e.g., Na, Al, Si, Mg, Ca) can be simultaneously determined. However, LASS-ICP-MS is superior over LA-MC-ICP-MS|OES, which is limited by its lower sensitivity. Moreover, LASS-ICP-MS offers trace element analysis down to the μg g(-1)-range for more than 28 elements due to lower limits of detection, and with typical uncertainties better than 15%. For in situ simultaneous

  11. In-situ Isotopic Analysis at Nanoscale using Parallel Ion Electron Spectrometry: A Powerful New Paradigm for Correlative Microscopy

    PubMed Central

    Yedra, Lluís; Eswara, Santhana; Dowsett, David; Wirtz, Tom

    2016-01-01

    Isotopic analysis is of paramount importance across the entire gamut of scientific research. To advance the frontiers of knowledge, a technique for nanoscale isotopic analysis is indispensable. Secondary Ion Mass Spectrometry (SIMS) is a well-established technique for analyzing isotopes, but its spatial-resolution is fundamentally limited. Transmission Electron Microscopy (TEM) is a well-known method for high-resolution imaging down to the atomic scale. However, isotopic analysis in TEM is not possible. Here, we introduce a powerful new paradigm for in-situ correlative microscopy called the Parallel Ion Electron Spectrometry by synergizing SIMS with TEM. We demonstrate this technique by distinguishing lithium carbonate nanoparticles according to the isotopic label of lithium, viz. 6Li and 7Li and imaging them at high-resolution by TEM, adding a new dimension to correlative microscopy. PMID:27350565

  12. In-situ Isotopic Analysis at Nanoscale using Parallel Ion Electron Spectrometry: A Powerful New Paradigm for Correlative Microscopy.

    PubMed

    Yedra, Lluís; Eswara, Santhana; Dowsett, David; Wirtz, Tom

    2016-01-01

    Isotopic analysis is of paramount importance across the entire gamut of scientific research. To advance the frontiers of knowledge, a technique for nanoscale isotopic analysis is indispensable. Secondary Ion Mass Spectrometry (SIMS) is a well-established technique for analyzing isotopes, but its spatial-resolution is fundamentally limited. Transmission Electron Microscopy (TEM) is a well-known method for high-resolution imaging down to the atomic scale. However, isotopic analysis in TEM is not possible. Here, we introduce a powerful new paradigm for in-situ correlative microscopy called the Parallel Ion Electron Spectrometry by synergizing SIMS with TEM. We demonstrate this technique by distinguishing lithium carbonate nanoparticles according to the isotopic label of lithium, viz. (6)Li and (7)Li and imaging them at high-resolution by TEM, adding a new dimension to correlative microscopy. PMID:27350565

  13. In-situ Isotopic Analysis at Nanoscale using Parallel Ion Electron Spectrometry: A Powerful New Paradigm for Correlative Microscopy

    NASA Astrophysics Data System (ADS)

    Yedra, Lluís; Eswara, Santhana; Dowsett, David; Wirtz, Tom

    2016-06-01

    Isotopic analysis is of paramount importance across the entire gamut of scientific research. To advance the frontiers of knowledge, a technique for nanoscale isotopic analysis is indispensable. Secondary Ion Mass Spectrometry (SIMS) is a well-established technique for analyzing isotopes, but its spatial-resolution is fundamentally limited. Transmission Electron Microscopy (TEM) is a well-known method for high-resolution imaging down to the atomic scale. However, isotopic analysis in TEM is not possible. Here, we introduce a powerful new paradigm for in-situ correlative microscopy called the Parallel Ion Electron Spectrometry by synergizing SIMS with TEM. We demonstrate this technique by distinguishing lithium carbonate nanoparticles according to the isotopic label of lithium, viz. 6Li and 7Li and imaging them at high-resolution by TEM, adding a new dimension to correlative microscopy.

  14. Isotope analysis of sulfur, bromine, and chlorine in individual anionic species by ion chromatography/multicollector-ICPMS.

    PubMed

    Zakon, Yevgeni; Halicz, Ludwik; Gelman, Faina

    2014-07-01

    We developed an analytical method for precise and accurate analysis of δ(34)S, δ(81)Br, and δ(37)Cl in individual anionic species by coupled ion chromatography (IC) and multicollector inductively coupled plasma mass spectrometry (MC-ICPMS). The method is based on the online separation and purification of ions by IC prior to their isotope analysis by MC-ICPMS. The developed technique significantly simplifies δ(34)S, δ(81)Br, and δ(37)Cl analysis in environmental samples. In cases when several anionic species of the same element are present in the sample, they might be analyzed in a single analytical run. Major isobaric interferences for the analyzed elements were reduced by using "dry" plasma conditions and applying sufficient mass resolution power. The sample-standard bracketing technique was used for instrumental drift correction. In the case of δ(34)S analysis, precisions up to 0.15‰ (1sd) have been achieved for analytes containing down to 5 nmol of S; for δ(81)Br, the attained precision was 0.1‰ (1sd) for analytes containing down to 0.6 nmol of Br. Precisions of 0.2‰ have been obtained for δ(37)Cl with analytes containing 0.7 μmol of Cl. Robustness of the developed analytical method, as well as high precisions and accuracies, has been demonstrated for the laboratory standard solutions and for environmental samples.

  15. Keratin decomposition by trogid beetles: evidence from a feeding experiment and stable isotope analysis

    NASA Astrophysics Data System (ADS)

    Sugiura, Shinji; Ikeda, Hiroshi

    2014-03-01

    The decomposition of vertebrate carcasses is an important ecosystem function. Soft tissues of dead vertebrates are rapidly decomposed by diverse animals. However, decomposition of hard tissues such as hairs and feathers is much slower because only a few animals can digest keratin, a protein that is concentrated in hairs and feathers. Although beetles of the family Trogidae are considered keratin feeders, their ecological function has rarely been explored. Here, we investigated the keratin-decomposition function of trogid beetles in heron-breeding colonies where keratin was frequently supplied as feathers. Three trogid species were collected from the colonies and observed feeding on heron feathers under laboratory conditions. We also measured the nitrogen (δ15N) and carbon (δ13C) stable isotope ratios of two trogid species that were maintained on a constant diet (feathers from one heron individual) during 70 days under laboratory conditions. We compared the isotopic signatures of the trogids with the feathers to investigate isotopic shifts from the feathers to the consumers for δ15N and δ13C. We used mixing models (MixSIR and SIAR) to estimate the main diets of individual field-collected trogid beetles. The analysis indicated that heron feathers were more important as food for trogid beetles than were soft tissues under field conditions. Together, the feeding experiment and stable isotope analysis provided strong evidence of keratin decomposition by trogid beetles.

  16. Stable isotope analysis of molecular oxygen from silicates and oxides using CO2 laser extraction

    NASA Technical Reports Server (NTRS)

    Perry, Eugene

    1996-01-01

    A laser-excited system for determination of the oxygen isotope composition of small quantities of silicate and oxide minerals was constructed and tested at JSC. This device is the first reported to use a commercially available helium cryostat to transfer and purify oxygen gas quantitatively within the system. The system uses oxygen gas instead of the conventional CO2 for mass spectrometer analyses. This modification of technique permits determination of all three stable oxygen isotopes, an essential requirement for oxygen isotope analysis of meteoritic material. Tests of the system included analysis of standard silicate materials NBS 28 and UWMG2 garnet, six SNC meteorites, and inclusions and chondrules from the Allende meteorite. Calibration with terrestrial standards was excellent. Meteorite values are close to published values and show no evidence of terrestrial oxygen contamination. The one limitation observed is that, in some runs on fine-grained SNC matrix material, sample results were affected by other samples in the sample holder within the reaction chamber. This reemphasizes the need for special precautions in dealing with fine-grained, reactive samples. Performance of the JSC instrument compares favorably with that of any other instrument currently producing published oxygen isotope data.

  17. Compound-Specific Stable Carbon Isotope Analysis of Chlorofluorocarbons in Groundwater.

    PubMed

    Horst, Axel; Lacrampe-Couloume, Georges; Sherwood Lollar, Barbara

    2015-10-20

    Chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs), controlled substances due to their role in stratospheric ozone loss, also occur as dissolved contaminants in groundwaters. Stable carbon isotopic signatures may provide valuable new information on the fate of these compounds as has been seen for other priority hydrocarbon contaminants, but to date no method for extraction and isotopic analysis of dissolved CFCs from groundwaters has been developed. Here we describe a cryogenic purge and trap system coupled to continuous flow compound-specific stable carbon isotope analysis mass spectrometry for concentrations as low as 35 μg/L. The method is validated by comparing isotopic signatures from water extracted CFCs against a new suite of isotopic CFC standards. Fractionation of CFCs in volatilization experiments from pure-phase CFC-11 and CFC-113 resulted in enrichment factors (ε) of +1.7 ± 0.1‰ and +1.1 ± 0.1‰, respectively, indicating that such volatile loss, if significant, would produce a more (13)C depleted signature in the remaining CFCs. Importantly, no significant fractionation was observed during volatile extraction of dissolved CFCs from aqueous solutions. δ(13)C values for groundwaters from a CFC-contaminated site were, on average, more enriched than δ(13)C values for pure compounds. Such enriched δ(13)C values have been seen in other hydrocarbon contaminants such as chlorinated ethenes and ethanes due to in situ degradation, but definitive interpretation of such enriched signatures in field samples requires additional experiments to characterize fractionation of CFCs during biodegradation. The establishment of a robust and sensitive method of extraction and analysis, as described here, provides the foundation for such future directions. PMID:26383531

  18. Compound-Specific Stable Carbon Isotope Analysis of Chlorofluorocarbons in Groundwater.

    PubMed

    Horst, Axel; Lacrampe-Couloume, Georges; Sherwood Lollar, Barbara

    2015-10-20

    Chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs), controlled substances due to their role in stratospheric ozone loss, also occur as dissolved contaminants in groundwaters. Stable carbon isotopic signatures may provide valuable new information on the fate of these compounds as has been seen for other priority hydrocarbon contaminants, but to date no method for extraction and isotopic analysis of dissolved CFCs from groundwaters has been developed. Here we describe a cryogenic purge and trap system coupled to continuous flow compound-specific stable carbon isotope analysis mass spectrometry for concentrations as low as 35 μg/L. The method is validated by comparing isotopic signatures from water extracted CFCs against a new suite of isotopic CFC standards. Fractionation of CFCs in volatilization experiments from pure-phase CFC-11 and CFC-113 resulted in enrichment factors (ε) of +1.7 ± 0.1‰ and +1.1 ± 0.1‰, respectively, indicating that such volatile loss, if significant, would produce a more (13)C depleted signature in the remaining CFCs. Importantly, no significant fractionation was observed during volatile extraction of dissolved CFCs from aqueous solutions. δ(13)C values for groundwaters from a CFC-contaminated site were, on average, more enriched than δ(13)C values for pure compounds. Such enriched δ(13)C values have been seen in other hydrocarbon contaminants such as chlorinated ethenes and ethanes due to in situ degradation, but definitive interpretation of such enriched signatures in field samples requires additional experiments to characterize fractionation of CFCs during biodegradation. The establishment of a robust and sensitive method of extraction and analysis, as described here, provides the foundation for such future directions.

  19. Use of Ga for mass bias correction for the accurate determination of copper isotope ratio in the NIST SRM 3114 Cu standard and geological samples by MC-ICP MS

    NASA Astrophysics Data System (ADS)

    Zhang, T.; Zhou, L.; Tong, S.

    2015-12-01

    The absolute determination of the Cu isotope ratio in NIST SRM 3114 based on a regression mass bias correction model is performed for the first time with NIST SRM 944 Ga as the calibrant. A value of 0.4471±0.0013 (2SD, n=37) for the 65Cu/63Cu ratio was obtained with a value of +0.18±0.04 ‰ (2SD, n=5) for δ65Cu relative to NIST 976.The availability of the NIST SRM 3114 material, now with the absolute value of the 65Cu/63Cu ratio and a δ65Cu value relative to NIST 976 makes it suitable as a new candidate reference material for Cu isotope studies. In addition, a protocol is described for the accurate and precise determination of δ65Cu values of geological reference materials. Purification of Cu from the sample matrix was performed using the AG MP-1M Bio-Rad resin. The column recovery for geological samples was found to be 100±2% (2SD, n=15).A modified method of standard-sample bracketing with internal normalization for mass bias correction was employed by adding natural Ga to both the sample and the solution of NIST SRM 3114, which was used as the bracketing standard. An absolute value of 0.4471±0.0013 (2SD, n=37) for 65Cu/63Cu quantified in this study was used to calibrate the 69Ga/71Ga ratio in the two adjacent bracketing standards of SRM 3114,their average value of 69Ga/71Ga was then used to correct the 65Cu/63Cu ratio in the sample. Measured δ65Cu values of 0.18±0.04‰ (2SD, n=20),0.13±0.04‰ (2SD, n=9),0.08±0.03‰ (2SD, n=6),0.01±0.06‰(2SD, n=4) and 0.26±0.04‰ (2SD, n=7) were obtained for five geological reference materials of BCR-2,BHVO-2,AGV-2,BIR-1a,and GSP-2,respectively,in agreement with values obtained in previous studies.

  20. Chromatographic speciation of Cr(III)-species, inter-species equilibrium isotope fractionation and improved chemical purification strategies for high-precision isotope analysis.

    PubMed

    Larsen, K K; Wielandt, D; Schiller, M; Bizzarro, M

    2016-04-22

    Chromatographic purification of chromium (Cr), which is required for high-precision isotope analysis, is complicated by the presence of multiple Cr-species with different effective charges in the acid digested sample aliquots. The differing ion exchange selectivity and sluggish reaction rates of these species can result in incomplete Cr recovery during chromatographic purification. Because of large mass-dependent inter-species isotope fractionation, incomplete recovery can affect the accuracy of high-precision Cr isotope analysis. Here, we demonstrate widely differing cation distribution coefficients of Cr(III)-species (Cr(3+), CrCl(2+) and CrCl2(+)) with equilibrium mass-dependent isotope fractionation spanning a range of ∼1‰/amu and consistent with theory. The heaviest isotopes partition into Cr(3+), intermediates in CrCl(2+) and the lightest in CrCl2(+)/CrCl3°. Thus, for a typical reported loss of ∼25% Cr (in the form of Cr(3+)) through chromatographic purification, this translates into 185 ppm/amu offset in the stable Cr isotope ratio of the residual sample. Depending on the validity of the mass-bias correction during isotope analysis, this further results in artificial mass-independent effects in the mass-bias corrected (53)Cr/(52)Cr (μ(53)Cr* of 5.2 ppm) and (54)Cr/(52)Cr (μ(54)Cr* of 13.5 ppm) components used to infer chronometric and nucleosynthetic information in meteorites. To mitigate these fractionation effects, we developed strategic chemical sample pre-treatment procedures that ensure high and reproducible Cr recovery. This is achieved either through 1) effective promotion of Cr(3+) by >5 days exposure to HNO3H2O2 solutions at room temperature, resulting in >∼98% Cr recovery for most types of sample matrices tested using a cationic chromatographic retention strategy, or 2) formation of Cr(III)-Cl complexes through exposure to concentrated HCl at high temperature (>120 °C) for several hours, resulting in >97.5% Cr recovery using a

  1. Chromatographic speciation of Cr(III)-species, inter-species equilibrium isotope fractionation and improved chemical purification strategies for high-precision isotope analysis

    PubMed Central

    Larsen, K.K.; Wielandt, D.; Schiller, M.; Bizzarro, M.

    2016-01-01

    Chromatographic purification of chromium (Cr), which is required for high-precision isotope analysis, is complicated by the presence of multiple Cr-species with different effective charges in the acid digested sample aliquots. The differing ion exchange selectivity and sluggish reaction rates of these species can result in incomplete Cr recovery during chromatographic purification. Because of large mass-dependent inter-species isotope fractionation, incomplete recovery can affect the accuracy of high-precision Cr isotope analysis. Here, we demonstrate widely differing cation distribution coefficients of Cr(III)-species (Cr3+, CrCl2+ and CrCl2+) with equilibrium mass-dependent isotope fractionation spanning a range of ~1‰/amu and consistent with theory. The heaviest isotopes partition into Cr3+, intermediates in CrCl2+ and the lightest in CrCl2+/CrCl3°. Thus, for a typical reported loss of ~25% Cr (in the form of Cr3+) through chromatographic purification, this translates into 185 ppm/amu offset in the stable Cr isotope ratio of the residual sample. Depending on the validity of the mass-bias correction during isotope analysis, this further results in artificial mass-independent effects in the mass-bias corrected 53Cr/52Cr (μ53 Cr* of 5.2 ppm) and 54Cr/52Cr (μ54Cr* of 13.5 ppm) components used to infer chronometric and nucleosynthetic information in meteorites. To mitigate these fractionation effects, we developed strategic chemical sample pre-treatment procedures that ensure high and reproducible Cr recovery. This is achieved either through 1) effective promotion of Cr3+ by >5 days exposure to HNO3 —H2O2 solutions at room temperature, resulting in >~98% Cr recovery for most types of sample matrices tested using a cationic chromatographic retention strategy, or 2) formation of Cr(III)-Cl complexes through exposure to concentrated HCl at high temperature (>120 °C) for several hours, resulting in >97.5% Cr recovery using a chromatographic elution strategy that

  2. Tungsten isotope analysis of meteorite samples using electrothermal vaporization (ETV)-MC-ICPMS technique

    NASA Astrophysics Data System (ADS)

    Okabayashi, S.; Sakata, S.; Hirata, T.

    2013-05-01

    Hf-W chronometer is based on the decay of 182Hf to 182W with a half-life of 8.9 ± 0.1 Myr. Hf is strongly lithophile elements, whereas W is moderately siderophile elements. Thus, the Hf-W age can provide critical information about the timing of metal-silicate differentiation (core formation) processes at the early stage of the planetary formation. Moreover, both the Hf and W is strongly refractory elements, the Hf-W age can reflect the timing of condensation or segregation of the metallic nuggets from chondritic reservoir at the early sequence of the solar system. The thermal ionization mass spectrometry (TIMS) is widely used for W isotope analysis. However, a micro-gram amount of W is desired for Hf-W chronological studies in this technique. The ICP-MS technique coupled with the conventional nebulization technique is also used for W isotope measurement. With this technique, total amount of W required for the isotopic ratio measurements could be 50 - 100 ng. On the other hand, typical ion transmission efficiency from sample to ion collector would be <0.1% under the sample introduction using the nebulizer. This suggests that the sample introduction efficiency (i.e., high transmission efficiency) can be dramatically improved when the loss of sample mist could be minimized. To achieve this, we have developed a sample introduction technique using the electrothermal vaporization (ETV) technique for W isotope analysis. In this study, W sample in 2% HNO3 solution is loaded on the Re filament located in a small volume ETV chamber to achieve minimum loss of W vapor and also to reduce the memory of W within the chamber. Temperature of the Re filament is controlled by the incident current (0 - 4 A). The W evaporation is carried out under the two different ambient gasses, Ar or He. We found that W signal intensity profile obtained under the Ar carrier gas is spiky and unstable, and this is not suitable for the precise isotopic analysis. In strike contrast, the signal

  3. Understanding N2O sources and sinks with laser based isotopic analysis

    NASA Astrophysics Data System (ADS)

    Mohn, Joachim; Harris, Eliza; Tuzson, Béla; Emmenegger, Lukas

    2015-04-01

    Nitrous oxide (N2O) is a potent greenhouse gas and the strongest ozone-destroying substance. The main emissions of N2O are linked to different microbial processes, therefore the sources are disperse and highly variable, complicating the development of effective mitigation strategies. Isotopic measurements have great potential to unravel spatial and temporal variations in sources, sinks and chemistry of N2O. Recent developments in quantum cascade laser spectroscopy (QCLAS) [1] allow both the intermolecular distribution of 15N substitutions ('site preference'; 15N14N16O versus 14N15N16O) and the oxygen isotopic composition (d18O) of N2O to be measured in real-time and at high precision of <0.2 ‰ [2]. Additionally, N2O isotopic analysis by QCLAS has demonstrated excellent compatibility to the standard technique isotope-ratio mass-spectrometry [3]. In a number of laboratory and pilot plant studies we investigated the isotopic signature of distinct microbial and abiotic N2O production and consumption pathways in soil and aqueous solution [e.g. 4]. Specific pathways were favoured by selection of the nitrogen substrates and process conditions and their isotopic signatures identified by real-time laser spectroscopic analysis. Results from our laboratory studies are in accordance with pure culture experiments and can therefore be applied to other ecosystems. Recently, high precision isotopic analysis at ambient N2O is also feasible by combining laser spectroscopy with automated preconcentration [5]. The field deployment was demonstrated by real-time monitoring isotopic composition of N2O emissions from an intensively managed grassland in central Switzerland for three months. The responses of the N2O isotopic signatures were analysed with respect to management events and weather influences [2]. In a follow-up project we intend to combine real-time N2O isotopic analysis at a tall tower in central Switzerland with atmospheric transport simulations and a biogeochemical model

  4. Isotopic Analysis of Fingernails as a USGS Open House Demonstration of the Use of Stable Isotopes in Foodweb Studies

    NASA Astrophysics Data System (ADS)

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

    2011-12-01

    The USGS Isotope Tracers Project uses stable isotopes and tritium to add a unique dimension of chemical information to a wide range of environmental investigations. The use and application of isotopes is usually an unfamiliar and even esoteric topic to the general public. Therefore during three USGS open house events, as a public outreach effort, we demonstrated the use of stable isotopes by analyzing nitrogen and carbon isotopes from very small fragments of fingernail from willing participants. We titled the exhibit "You Are What You Eat". The results from all participants were plotted on a graph indicating the general influence of different food groups on the composition of body tissues as represented by fingernails. All participants were assigned a number and no personal-identification information was collected. A subset of participants provided us with an estimate of the number of days a week various foods were eaten and if they were vegetarians, vegans or non-vegetarians. Volunteers from our research group were on hand to explain and discuss fundamental concepts such as how foods attain their isotopic composition, the difference between C3 and C4 plants, the effects of assimilation, trophic enrichment, and the various uses of stable isotopes in environmental studies. The results of the fingernail analyses showed the variation of the range of isotopic compositions among about 400 people at each event, the distinct influence of C4 plants (mainly corn and cane sugar) on our carbon isotopic composition, and the isotopic differences between vegetarians and non vegetarians among other details (http://wwwrcamnl.wr.usgs.gov/isoig/projects/fingernails/). A poll of visitors attending the open house event in 2006 indicated that "You Are What You Eat" was among the most popular exhibits. Following the first two open house events we were contacted by a group of researchers from Brazil who had completed a very similar study. Our collaboration resulted in a publication in

  5. Accurate Analysis of the Change in Volume, Location, and Shape of Metastatic Cervical Lymph Nodes During Radiotherapy

    SciTech Connect

    Takao, Seishin; Tadano, Shigeru; Taguchi, Hiroshi; Yasuda, Koichi; Onimaru, Rikiya; Ishikawa, Masayori; Bengua, Gerard; Suzuki, Ryusuke; Shirato, Hiroki

    2011-11-01

    Purpose: To establish a method for the accurate acquisition and analysis of the variations in tumor volume, location, and three-dimensional (3D) shape of tumors during radiotherapy in the era of image-guided radiotherapy. Methods and Materials: Finite element models of lymph nodes were developed based on computed tomography (CT) images taken before the start of treatment and every week during the treatment period. A surface geometry map with a volumetric scale was adopted and used for the analysis. Six metastatic cervical lymph nodes, 3.5 to 55.1 cm{sup 3} before treatment, in 6 patients with head and neck carcinomas were analyzed in this study. Three fiducial markers implanted in mouthpieces were used for the fusion of CT images. Changes in the location of the lymph nodes were measured on the basis of these fiducial markers. Results: The surface geometry maps showed convex regions in red and concave regions in blue to ensure that the characteristics of the 3D tumor geometries are simply understood visually. After the irradiation of 66 to 70 Gy in 2 Gy daily doses, the patterns of the colors had not changed significantly, and the maps before and during treatment were strongly correlated (average correlation coefficient was 0.808), suggesting that the tumors shrank uniformly, maintaining the original characteristics of the shapes in all 6 patients. The movement of the gravitational center of the lymph nodes during the treatment period was everywhere less than {+-}5 mm except in 1 patient, in whom the change reached nearly 10 mm. Conclusions: The surface geometry map was useful for an accurate evaluation of the changes in volume and 3D shapes of metastatic lymph nodes. The fusion of the initial and follow-up CT images based on fiducial markers enabled an analysis of changes in the location of the targets. Metastatic cervical lymph nodes in patients were suggested to decrease in size without significant changes in the 3D shape during radiotherapy. The movements of the

  6. Quantifying Inter-Laboratory Variability in Stable Isotope Analysis of Ancient Skeletal Remains

    PubMed Central

    Pestle, William J.; Crowley, Brooke E.; Weirauch, Matthew T.

    2014-01-01

    Over the past forty years, stable isotope analysis of bone (and tooth) collagen and hydroxyapatite has become a mainstay of archaeological and paleoanthropological reconstructions of paleodiet and paleoenvironment. Despite this method's frequent use across anthropological subdisciplines (and beyond), the present work represents the first attempt at gauging the effects of inter-laboratory variability engendered by differences in a) sample preparation, and b) analysis (instrumentation, working standards, and data calibration). Replicate analyses of a 14C-dated ancient human bone by twenty-one archaeological and paleoecological stable isotope laboratories revealed significant inter-laboratory isotopic variation for both collagen and carbonate. For bone collagen, we found a sizeable range of 1.8‰ for δ13Ccol and 1.9‰ for δ15Ncol among laboratories, but an interpretatively insignificant average pairwise difference of 0.2‰ and 0.4‰ for δ13Ccol and δ15Ncol respectively. For bone hydroxyapatite the observed range increased to a troublingly large 3.5‰ for δ13Cap and 6.7‰ for δ18Oap, with average pairwise differences of 0.6‰ for δ13Cap and a disquieting 2.0‰ for δ18Oap. In order to assess the effects of preparation versus analysis on isotopic variability among laboratories, a subset of the samples prepared by the participating laboratories were analyzed a second time on the same instrument. Based on this duplicate analysis, it was determined that roughly half of the isotopic variability among laboratories could be attributed to differences in sample preparation, with the other half resulting from differences in analysis (instrumentation, working standards, and data calibration). These findings have serious implications for choices made in the preparation and extraction of target biomolecules, the comparison of results obtained from different laboratories, and the interpretation of small differences in bone collagen and hydroxyapatite isotope values

  7. Light Isotopes and Trace Organics Analysis of Mars Samples with Mass Spectrometry

    NASA Technical Reports Server (NTRS)

    Mahaffy, P.; Niemann, Hasso (Technical Monitor)

    2001-01-01

    Precision measurement of light isotopes in Mars surface minerals and comparison of this isotopic composition with atmospheric gas and other, well-mixed reservoirs such as surface dust are necessary to understand the history of atmospheric evolution from a possibly warmer and wetter Martian surface to the present state. Atmospheric sources and sinks that set these ratios are volcanism, solar wind sputtering, photochemical processes, and weathering. Measurement of a range of trace organic species with a particular focus on species such as amino acids that are the building blocks of terrestrial life are likewise important to address the questions of prebiotic and present or past biological activity on Mars. The workshop topics "isotopic mineralogy" and "biology and pre-biotic chemistry" will be addressed from the point of view of the capabilities and limitations of insitu mass spectrometry (MS) techniques such as thermally evolved gas analysis (TEGA) and gas chromatography (GC) surface experiments using MS, in both cases, as a final chemical and isotopic composition detector. Insitu experiments using straightforward adaptations of existing space proven hardware can provide a substantial improvement in the precision and accuracy of our present knowledge of isotopic composition both in molecular and atomic species in the atmosphere and those chemically bound in rocks and soils. Likewise, detection of trace organic species with greatly improved sensitivity from the Viking GCMS experiment is possible using gas enrichment techniques. The limits to precision and accuracy of presently feasible insitu techniques compared to laboratory analysis of returned samples will be explored. The insitu techniques are sufficiently powerful that they can provide a high fidelity method of screening samples obtained from a diverse set of surface locations such as the subsurface or the interior of rocks for selection of those that are the most interesting for return to Earth.

  8. A refined sampling strategy for intra-tooth stable isotope analysis of mammalian enamel

    NASA Astrophysics Data System (ADS)

    Zazzo, A.; Bendrey, R.; Vella, D.; Moloney, A. P.; Monahan, F. J.; Schmidt, O.

    2012-05-01

    Serial sampling and stable isotope analysis performed along the growth axis of vertebrate tooth enamel records differences attributed to seasonal variation in diet, climate or animal movement. Because several months are required to obtain mature enamel in large mammals, modifications in the isotopic composition of environmental parameters are not instantaneously recorded, and stable isotope analysis of tooth enamel returns a time-averaged signal attenuated in its amplitude relative to the input signal. For convenience, stable isotope profiles are usually determined on the side of the tooth where enamel is thickest. Here we investigate the possibility of improving the time resolution by targeting the side of the tooth where enamel is thinnest. Observation of developing third molars (M3) in sheep shows that the tooth growth rate is not constant but decreases exponentially, while the angle between the first layer of enamel deposited and the enamel-dentine junction increases as a tooth approaches its maximal length. We also noted differences in thickness and geometry of enamel growth between the mesial side (i.e., the side facing the M2) and the buccal side (i.e., the side facing the cheek) of the M3. Carbon and oxygen isotope variations were measured along the M3 teeth from eight sheep raised under controlled conditions. Intra-tooth variability was systematically larger along the mesial side and the difference in amplitude between the two sides was proportional to the time of exposure to the input signal. Although attenuated, the mesial side records variations in the environmental signal more faithfully than the buccal side. This approach can be adapted to other mammals whose teeth show lateral variation in enamel thickness and could potentially be used as an internal check for diagenesis.

  9. Technical Note: A simple method for vaterite precipitation in isotopic equilibrium: implications for bulk and clumped isotope analysis

    NASA Astrophysics Data System (ADS)

    Kluge, T.; John, C. M.

    2014-12-01

    Calcium carbonate (CaCO3) plays an important role in the natural environment as a major constituent of the skeleton and supporting structure of marine life and has high economic importance as additive in food, chemicals and medical products. Pure CaCO3 occurs in the three different polymorphs calcite, aragonite and vaterite, whereof calcite is the most abundant and best characterized mineral. In contrast, little is known about the rare polymorph vaterite, in particular with regard to the oxygen isotope fractionation between H2O and the mineral. Synthetic precipitation of vaterite in the laboratory typically involves rapid processes and isotopic non-equilibrium, which excludes isotope studies focused on characterization of vaterite at equilibrium conditions. Here, we used a new experimental approach that enables vaterite mineral formation from an isotopically equilibrated solution. The solution consists of a ~ 0.007 mol L-1 CaCO3 solution that is saturated with NaCl at room temperature (up to 6.5 mol L-1). Vaterite precipitated as single phase or major phase (≥ 94%) in experiments performed between 23 and 91 °C. Only at 80 °C was vaterite a minor phase with a relative abundance of 27%. The high mineral yield of up to 235 mg relative to a total dissolved CaCO3 amount of 370 mg enables an investigation of the oxygen isotope fractionation between mineral and water, and the determination of clumped isotope values in vaterite.

  10. Entropy analysis of stable isotopes in precipitation: tracing the monsoon systems in China

    NASA Astrophysics Data System (ADS)

    Wang, Tao; Chen, Jiansheng; Li, Ling

    2016-08-01

    Due to the complexity of monsoon systems and random behaviors of isotope tracers, conventional methods are not adequate for uncovering detailed information about monsoon activities from typically limited precipitation isotope data. We developed a new approach based on the entropy theory to analyze such data with a focus on the monsoon systems in China, dealing with the complexity of these systems and data deficiency. Using precipitation isotope data from 42 selected stations in and around China within the GNIP network, we computed entropies associated with D and 18O. These entropies were found to relate linearly to each other with a proportionality factor close to unity. The spatial variations of the D and 18O entropy in the study area revealed the origins, extents and pathways of the Chinese monsoon systems, as well as their interactions. While further investigation is needed at a greater (global) scale, this study has demonstrated how the entropy theory enables an in-depth analysis of precipitation isotope data to trace the pathway and determine the range of a monsoon system.

  11. Entropy analysis of stable isotopes in precipitation: tracing the monsoon systems in China

    PubMed Central

    Wang, Tao; Chen, Jiansheng; Li, Ling

    2016-01-01

    Due to the complexity of monsoon systems and random behaviors of isotope tracers, conventional methods are not adequate for uncovering detailed information about monsoon activities from typically limited precipitation isotope data. We developed a new approach based on the entropy theory to analyze such data with a focus on the monsoon systems in China, dealing with the complexity of these systems and data deficiency. Using precipitation isotope data from 42 selected stations in and around China within the GNIP network, we computed entropies associated with D and 18O. These entropies were found to relate linearly to each other with a proportionality factor close to unity. The spatial variations of the D and 18O entropy in the study area revealed the origins, extents and pathways of the Chinese monsoon systems, as well as their interactions. While further investigation is needed at a greater (global) scale, this study has demonstrated how the entropy theory enables an in-depth analysis of precipitation isotope data to trace the pathway and determine the range of a monsoon system. PMID:27507656

  12. Comparing evapotranspiration partitioning after different types of rain events using stable isotopes and lagrangian dispersion analysis

    NASA Astrophysics Data System (ADS)

    Hogan, Patrick; Parajka, Juraj

    2016-04-01

    The eddy covariance method has become one of the standard methods for measuring evapotranspiration (ET) at the field scale, however it cannot separate transpiration from evaporation and it is also limited within plant canopies due to distortion of the turbulent wind fields. Possible solutions to these limitations include combining EC measurements made above the canopy coupled with either source/sink distribution models or stable isotope ET partitioning models. During the summer of 2014 the concentration and isotopic ratio of water vapour within the canopy of a growing maize field at the Hydrological Open Air Laboratory (HOAL) catchment was measured using a Picarro field sampling device. A tripod mounted eddy covariance device was used to calculate the ET value for the field. The first objective of this experiment is to compare the ET partitioning results made using the stable isotope Keeling Plot method within a canopy to two different lagrangian dispersion analysis methods, the Localised Near Field theory of Raupach (1989a) and the Warland and Thurtell (2000) dispersion model. Preliminary results show good agreement during dry conditions with the dispersion methods overestimating the fraction of transpiration directly after a rain event. The second objective is then to analyse and compare the soil evaporation response for two different kinds of rain events using the stable isotope results.

  13. Entropy analysis of stable isotopes in precipitation: tracing the monsoon systems in China.

    PubMed

    Wang, Tao; Chen, Jiansheng; Li, Ling

    2016-01-01

    Due to the complexity of monsoon systems and random behaviors of isotope tracers, conventional methods are not adequate for uncovering detailed information about monsoon activities from typically limited precipitation isotope data. We developed a new approach based on the entropy theory to analyze such data with a focus on the monsoon systems in China, dealing with the complexity of these systems and data deficiency. Using precipitation isotope data from 42 selected stations in and around China within the GNIP network, we computed entropies associated with D and (18)O. These entropies were found to relate linearly to each other with a proportionality factor close to unity. The spatial variations of the D and (18)O entropy in the study area revealed the origins, extents and pathways of the Chinese monsoon systems, as well as their interactions. While further investigation is needed at a greater (global) scale, this study has demonstrated how the entropy theory enables an in-depth analysis of precipitation isotope data to trace the pathway and determine the range of a monsoon system. PMID:27507656

  14. Entropy analysis of stable isotopes in precipitation: tracing the monsoon systems in China.

    PubMed

    Wang, Tao; Chen, Jiansheng; Li, Ling

    2016-08-10

    Due to the complexity of monsoon systems and random behaviors of isotope tracers, conventional methods are not adequate for uncovering detailed information about monsoon activities from typically limited precipitation isotope data. We developed a new approach based on the entropy theory to analyze such data with a focus on the monsoon systems in China, dealing with the complexity of these systems and data deficiency. Using precipitation isotope data from 42 selected stations in and around China within the GNIP network, we computed entropies associated with D and (18)O. These entropies were found to relate linearly to each other with a proportionality factor close to unity. The spatial variations of the D and (18)O entropy in the study area revealed the origins, extents and pathways of the Chinese monsoon systems, as well as their interactions. While further investigation is needed at a greater (global) scale, this study has demonstrated how the entropy theory enables an in-depth analysis of precipitation isotope data to trace the pathway and determine the range of a monsoon system.

  15. Ancient bronze coins from Mediterranean basin: LAMQS potentiality for lead isotopes comparative analysis with former mineral

    NASA Astrophysics Data System (ADS)

    Torrisi, L.; Italiano, A.; Torrisi, A.

    2016-11-01

    Bronze coins coming from the area of the Mediterranean basin, dated back the II-X Cent. A.D., were analyzed using different physical analytical techniques. Characteristic X-ray fluorescence was used with electrons and photons, in order to investigate the elemental composition of both the surface layers and bulk. Moreover, the quadrupole mass spectrometry coupled to laser ablation (LAMQS technique) in high vacuum was used to analyse typical material compounds from surface contamination. Mass spectrometry, at high resolution and sensitivity, extended up to 300 amu, allowed measuring the 208Pb/206Pb and 207Pb/206Pb isotopic ratios into the coins. Quantitative relative analyses of these isotopic ratios identify the coin composition such as a "fingerprint" depending on the mineral used to extract the lead. Isotopic ratios in coins can be compared to those of the possible minerals used to produce the bronze alloy. A comparison between the measured isotope ratios in the analyzed coins and the literature database, related to the mineral containing Pb as a function of its geological and geophysical extraction mine, is presented. The analysis, restricted to old coins and the mines of the Mediterranean basin, indicates a possible correlation between the coin compositions and the possible geological sites of the extracted mineral.

  16. Source apportionment of aerosol iron in the marine environment using iron isotope analysis

    NASA Astrophysics Data System (ADS)

    Mead, Chris; Herckes, Pierre; Majestic, Brian J.; Anbar, Ariel D.

    2013-11-01

    (Fe) is a critical nutrient for phytoplankton. In the open ocean, this demand coupled with scarce supply often makes Fe the limiting factor in phytoplankton growth. The largest source, by mass, of Fe to the open ocean is windblown soil dust, but this Fe is much less soluble than Fe from other aerosol sources. Therefore, to fully understand how Fe reaches this ecosystem, it is necessary to understand the range of sources of aerosol Fe. To do this, we collected size-segregated aerosol samples from Bermuda and analyzed them to determine their Fe isotope composition. From this analysis, we found clear evidence in the fine size fraction (< 2.5 µm) of an important non-soil-dust Fe source. Our isotope analysis of multiple oil and coal fly ashes shows that those materials cannot explain our finding. We suggest biomass burning as the most likely source.

  17. Authentication of fishery and aquaculture products by multi-element and stable isotope analysis.

    PubMed

    Li, Li; Boyd, Claude E; Sun, Zhenlong

    2016-03-01

    The market of fishery and aquaculture products is globalized with increasing numbers of mislabeled products. This highlights the need for approaches to indentify the origin of these products. Among the measures used to identify the origin of other agro-products, multi-element and stable isotope analysis are promising approaches to identify the authenticity and traceability of fishery and aquaculture products. The present paper reviews the use of multi-element and stable isotope analysis to determine the origin of fishery and aquaculture products. Principles and limitations of each method will be illustrated and perspectives for traceability of fishery and aquaculture products will be discussed. The aim of this review is to mediate fundamental knowledge for the interpretation of experimental data on authentication of aquaculture products.

  18. Authentication of fishery and aquaculture products by multi-element and stable isotope analysis.

    PubMed

    Li, Li; Boyd, Claude E; Sun, Zhenlong

    2016-03-01

    The market of fishery and aquaculture products is globalized with increasing numbers of mislabeled products. This highlights the need for approaches to indentify the origin of these products. Among the measures used to identify the origin of other agro-products, multi-element and stable isotope analysis are promising approaches to identify the authenticity and traceability of fishery and aquaculture products. The present paper reviews the use of multi-element and stable isotope analysis to determine the origin of fishery and aquaculture products. Principles and limitations of each method will be illustrated and perspectives for traceability of fishery and aquaculture products will be discussed. The aim of this review is to mediate fundamental knowledge for the interpretation of experimental data on authentication of aquaculture products. PMID:26471677

  19. Gamma isotopic analysis of the coals and ashes from coal fired power plants of Turkey

    NASA Astrophysics Data System (ADS)

    Akyuz, T.; Varinlioglu, A.; Kose, A.

    1999-01-01

    Gamma-isotopic analysis of the ashes produced by the combustion of lignite in power stations of Turkey together with the parent coal samples was performed with the aim to estimate its potential adverse impacts on human health. Gamma-isotopic analysis indicated that all samples contained226Ra (coal samples: 89 148 Bq kg-1; ash samples: 15 26 Bq kg-1),238U (coal samples: 2 4 μg g-1; ash samples: 9 33 μg g-1),232Th (coal samples: 1 9 μg g-1; ash samples: 8 12μg g-1), and40K (coal samples: 26 67 Bq kg-1; ash samples: not detected).134Cs and137Cs have not been found in the samples.

  20. Gamma isotopic analysis of the coals and ashes from coal fired power plants of Turkey

    NASA Astrophysics Data System (ADS)

    Akyuz, T.; Varinlioglu, A.; Kose, A.

    1999-01-01

    Gamma-isotopic analysis of the ashes produced by the combustion of lignite in power stations of Turkey together with the parent coal samples was performed with the aim to estimate its potential adverse impacts on human health. Gamma-isotopic analysis indicated that all samples contained226Ra (coal samples: 89-148 Bq kg-1; ash samples: 15-26 Bq kg-1),238U (coal samples: 2-4 μg g-1; ash samples: 9-33 μg g-1),232Th (coal samples: 1-9 μg g-1; ash samples: 8-12μg g-1), and40K (coal samples: 26-67 Bq kg-1; ash samples: not detected).134Cs and137Cs have not been found in the samples.

  1. A novel isotope analysis of oxygen in uranium oxides: comparison of secondary ion mass spectrometry, glow discharge mass spectrometry and thermal ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Pajo, L.; Tamborini, G.; Rasmussen, G.; Mayer, K.; Koch, L.

    2001-05-01

    The natural variation of the oxygen isotopic composition is used among geologists to determine paleotemperatures and the origin of minerals. In recent studies, oxygen isotopic composition has been recognized as a possible tool for identification of the origin of seized uranium oxides in nuclear forensic science. In the last 10 years, great effort has been made to develop new direct and accurate n( 18O)/ n( 16O) measurements methods. Traditionally, n( 18O)/ n( 16O) analyses are performed by gas mass spectrometry. In this work, a novel oxygen isotope analysis by thermal ionization mass spectrometry (TIMS), using metal oxide ion species (UO +), is compared to the direct methods: glow discharge mass spectrometry (GDMS) and secondary ion mass spectrometry (SIMS). Because of the possible application of the n( 18O)/ n( 16O) ratio in nuclear forensics science, the samples were solid, pure UO 2 or U 3O 8 particles. The precision achieved using TIMS analysis was 0.04%, which is similar or even better than the one obtained using the SIMS technique (0.05%), and clearly better if compared to that of GDMS (0.5%). The samples used by TIMS are micrograms in size. The suitability of TIMS as a n( 18O)/ n( 16O) measurement method is verified by SIMS measurements. In addition, TIMS results have been confirmed by characterizing the n( 18O)/ n( 16O) ratio of UO 2 sample also by the traditional method of static vacuum mass spectrometry at the University of Chicago.

  2. Contrasting behavior of oxygen and iron isotopes in banded iron formation revealed by in situ analysis

    NASA Astrophysics Data System (ADS)

    Beard, B.; Li, W.; Kita, N.; Valley, J. W.; Johnson, C.

    2012-12-01

    Banded iron formations (BIFs) record a period of dramatic secular change in Earth's geologic history, when abundant aqueous Fe(II) was removed from Archean and Proterozoic oceans by oxidation. BIFs are characterized by co-existing of quartz and iron minerals, including oxides and carbonates, and alternating iron-rich and iron-poor layers range from m to isotope ratios in minerals in BIFs provide valuable information about the origin of BIFs, as well as diagenetic and metamorphic effects that were superimposed on primary layering. We analyzed O and Fe isotope compositions of magnetite and hematite in BIFs from the 2.5 Ga Dales Gorge Member of the Brockman Iron Formation, Hamersley Group, Western Australia. Oxygen isotope ratios were measured by Secondary Ion Mass Spectrometry (SIMS), and Fe isotope ratios were measured by femtosecond Laser ablation Multi-Collector ICP-MS (fs-LA-MC-ICP-MS), with spatial resolutions of 15 mm (O) and 30-50 mm (Fe), and external precisions (2s) of +0.7 ‰ for δ18O and +0.2 ‰ for δ56Fe, respectively. Analysis of δ18O in iron oxides by SIMS employed special tuning with a 3kV primary beam to minimize orientation effects (Huberty et al. 2010 ). For hematite, δ18O values range from -7.1 ‰ to -0.6 ‰, with the majority of data clustering around -4.5 ‰, and δ56Fe values range from -0.50 ‰ to +1.53‰. Magnetite has a δ18O range of -5.6 ‰ to +5.6 ‰ and a δ56Fe range of -0.76 ‰ to +1.33 ‰. Notably, magnetite shows significant O isotope heterogeneity at a mineral grain scale, and the highest δ18O values were commonly measured from Si-rich (1-3 wt% SiO2) magnetite overgrowths or magnetite grains that have a recrystallization texture. In contrast, lowest δ18O values were measured from magnetite that contains less than 1 wt% SiO2. Individual magnetite grains can have up to 6 ‰ variation in δ18O values between low-Si core and Si-rich overgrowth. Iron

  3. Evaluating gull diets: A comparison of conventional methods and stable isotope analysis

    USGS Publications Warehouse

    Weiser, E.L.; Powell, A.N.

    2011-01-01

    Samples such as regurgitated pellets and food remains have traditionally been used in studies of bird diets, but these can produce biased estimates depending on the digestibility of different foods. Stable isotope analysis has been developed as a method for assessing bird diets that is not biased by digestibility. These two methods may provide complementary or conflicting information on diets of birds, but are rarely compared directly. We analyzed carbon and nitrogen stable isotope ratios of feathers of Glaucous Gull (Larus hyperboreus) chicks from eight breeding colonies in northern Alaska, and used a Bayesian mixing model to generate a probability distribution for the contribution of each food group to diets. We compared these model results with probability distributions from conventional diet samples (pellets and food remains) from the same colonies and time periods. Relative to the stable isotope estimates, conventional analysis often overestimated the contributions of birds and small mammals to gull diets and often underestimated the contributions of fish and zooplankton. Both methods gave similar estimates for the contributions of scavenged caribou, miscellaneous marine foods, and garbage to diets. Pellets and food remains therefore may be useful for assessing the importance of garbage relative to certain other foods in diets of gulls and similar birds, but are clearly inappropriate for estimating the potential impact of gulls on birds, small mammals, or fish. However, conventional samples provide more species-level information than stable isotope analysis, so a combined approach would be most useful for diet analysis and assessing a predator's impact on particular prey groups. ?? 2011 Association of Field Ornithologists.

  4. Quantifying RDX biodegradation in groundwater using delta15N isotope analysis.

    PubMed

    Bernstein, Anat; Adar, Eilon; Ronen, Zeev; Lowag, Harald; Stichler, Willibald; Meckenstock, Rainer U

    2010-01-15

    Isotope analysis was used to examine the extent of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) biodegradation in groundwater along a ca. 1.35-km contamination plume. Biodegradation was proposed as a natural attenuating remediation method for the contaminated aquifer. By isotope analysis of RDX, the extent of biodegradation was found to reach up to 99.5% of the initial mass at a distance of 1.15-1.35km down gradient from the contamination sources. A range of first-order biodegradation rates was calculated based on the degradation extents, with average half-life values ranging between 4.4 and 12.8years for RDX biodegradation in the upper 15m of the aquifer, assuming purely aerobic biodegradation, and between 10.9 and 31.2years, assuming purely anaerobic biodegradation. Based on the geochemical data, an aerobic biodegradation pathway was suggested as the dominant attenuation process at the site. The calculated biodegradation rate was correlated with depth, showing decreasing degradation rates in deeper groundwater layers. Exceptionally low first-order kinetic constants were found in a borehole penetrating the bottom of the aquifer, with half life ranging between 85.0 to 161.5years, assuming purely aerobic biodegradation, and between 207.5 and 394.3years, assuming purely anaerobic biodegradation. The study showed that stable isotope fractionation analysis is a suitable tool to detect biodegradation of RDX in the environment. Our findings clearly indicated that RDX is naturally biodegraded in the contaminated aquifer. To the best of our knowledge, this is the first reported use of RDX isotope analysis to quantify its biodegradation in contaminated aquifers.

  5. Use of New 1013 Ohm Current Amplifiers in U and Pb Isotope Ratio Analysis by TIMS

    NASA Astrophysics Data System (ADS)

    Bouman, C.; Trinquier, A.; Lloyd, N. S.; Schwieters, J. B.

    2014-12-01

    Faraday cups can potentially be improved by a factor of 10 too. This presentation will focus on the analysis of small Pb and U using TIMS, for geochronology and nuclear forensics. In our setup, all U and Pb isotopes are measured simultaneously on Faraday cups, except 204Pb which is collected on the SEM since the 204Pb is the least abundant and required for common lead correction.

  6. Diagnosis of medium chain acyl-CoA dehydrogenase deficiency by stable isotope dilution analysis of urinary acylglycines: Retrospective and prospective studies, and comparison of its accuracy to acylcarnitine identification by FAB/mass spectrometry

    SciTech Connect

    Rinaldo, P.; O'Shea, J.J.; Welch, R.D.; Tanaka, K. )

    1990-01-01

    In summary, we have demonstrated that the accurate quantitation of urinary HG and PPG by stable isotope dilution analysis is currently the most reliable method for the diagnosis of MCAD deficiency. This method is particularly useful for testing random samples from asymptomatic patients without any provocative test, and it is suitable to widely survey a fairly large population, such as patients with episodic manifestations and families with a history of SIDS.

  7. Trace, isotopic analysis of micron-sized grains -- Mo, Zr analysis of stardust (SiC and graphite grains).

    SciTech Connect

    Pellin, M. J.; Nicolussi, G. K.

    1998-02-19

    Secondary Neutral Mass Spectrometry using resonant laser ionization can provide for both high useful yields and high discrimination while maintaining high lateral and depth resolutions. An example of the power of the method is measurement of the isotopic composition of Mo and Zr in 1-5 {micro}m presolar SiC and graphite grains isolated from the Murchison CM2 meteorite for the first time. These grains have survived the formation of the Solar System and isotopic analysis reveals a record of the stellar nucleosynthesis present during their formation. Mo and Zr, though present at less than 10 ppm in some grains, are particularly useful in that among their isotopes are members that can only be formed by distinct nucleosynthetic processes known as s-, p-, and r-process. Successful isotopic analysis of these elements requires both high selectivity (since these are trace elements) and high efficiency (since the total number of atoms available are limited). Resonant Ionization Spectroscopy is particularly useful and flexible in this application. While the sensitivity of this t.edmique has often been reported in the past, we focus hereon the very low noise properties of the technique. We further demonstrate the efficacy of noise removal by two complimentary methods. First we use the resonant nature of the signal to subtract background signal. Second we demonstrate that by choosing the appropriate resonance scheme background can often be dramatically reduced.

  8. Optimizing sample pretreatment for compound-specific stable carbon isotopic analysis of amino sugars in marine sediment

    NASA Astrophysics Data System (ADS)

    Zhu, R.; Lin, Y.-S.; Lipp, J. S.; Meador, T. B.; Hinrichs, K.-U.

    2014-09-01

    Amino sugars are quantitatively significant constituents of soil and marine sediment, but their sources and turnover in environmental samples remain poorly understood. The stable carbon isotopic composition of amino sugars can provide information on the lifestyles of their source organisms and can be monitored during incubations with labeled substrates to estimate the turnover rates of microbial populations. However, until now, such investigation has been carried out only with soil samples, partly because of the much lower abundance of amino sugars in marine environments. We therefore optimized a procedure for compound-specific isotopic analysis of amino sugars in marine sediment, employing gas chromatography-isotope ratio mass spectrometry. The whole procedure consisted of hydrolysis, neutralization, enrichment, and derivatization of amino sugars. Except for the derivatization step, the protocol introduced negligible isotopic fractionation, and the minimum requirement of amino sugar for isotopic analysis was 20 ng, i.e., equivalent to ~8 ng of amino sugar carbon. Compound-specific stable carbon isotopic analysis of amino sugars obtained from marine sediment extracts indicated that glucosamine and galactosamine were mainly derived from organic detritus, whereas muramic acid showed isotopic imprints from indigenous bacterial activities. The δ13C analysis of amino sugars provides a valuable addition to the biomarker-based characterization of microbial metabolism in the deep marine biosphere, which so far has been lipid oriented and biased towards the detection of archaeal signals.

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

    NASA Astrophysics Data System (ADS)

    Thompson, Reece

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

  10. Tracing fetal and childhood exposure to lead using isotope analysis of deciduous teeth.

    PubMed

    Shepherd, Thomas J; Dirks, Wendy; Roberts, Nick M W; Patel, Jaiminkumar G; Hodgson, Susan; Pless-Mulloli, Tanja; Walton, Pamela; Parrish, Randall R

    2016-04-01

    We report progress in using the isotopic composition and concentration of Pb in the dentine and enamel of deciduous teeth to provide a high resolution time frame of exposure to Pb during fetal development and early childhood. Isotope measurements (total Pb and (208)Pb/(206)Pb, (207)Pb/(206)Pb ratios) were acquired by laser ablation inductively coupled mass spectrometry at contiguous 100 micron intervals across thin sections of the teeth; from the outer enamel surface to the pulp cavity. Teeth samples (n=10) were selected from two cohorts of children, aged 5-8 years, living in NE England. By integrating the isotope data with histological analysis of the teeth, using the daily incremental lines in dentine, we were able to assign true estimated ages to each ablation point (first 2-3 years for molars, first 1-2 years for incisors+pre-natal growth). Significant differences were observed in the isotope composition and concentration of Pb between children, reflecting differences in the timing and sources of exposure during early childhood. Those born in 2000, after the withdrawal of leaded petrol in 1999, have the lowest dentine Pb levels (<0.2µgPb/g) with (208)Pb/(206)Pb (mean ±2σ: 2.126-2.079) (208)Pb/(206)Pb (mean ±2σ: 0.879-0.856) ratios that correlate very closely with modern day Western European industrial aerosols (PM10, PM2.5) suggesting that diffuse airborne pollution was probably the primary source and exposure pathway. Legacy lead, if present, is insignificant. For those born in 1997, dentine lead levels are typically higher (>0.4µgPb/g) with (208)Pb/(206)Pb (mean ±2σ: 2.145-2.117) (208)Pb/(206)Pb (mean ±2σ: 0.898-0.882) ratios that can be modelled as a binary mix between industrial aerosols and leaded petrol emissions. Short duration, high intensity exposure events (1-2 months) were readily identified, together with evidence that dentine provides a good proxy for childhood changes in the isotope composition of blood Pb. Our pilot study confirms that

  11. Tracing fetal and childhood exposure to lead using isotope analysis of deciduous teeth.

    PubMed

    Shepherd, Thomas J; Dirks, Wendy; Roberts, Nick M W; Patel, Jaiminkumar G; Hodgson, Susan; Pless-Mulloli, Tanja; Walton, Pamela; Parrish, Randall R

    2016-04-01

    We report progress in using the isotopic composition and concentration of Pb in the dentine and enamel of deciduous teeth to provide a high resolution time frame of exposure to Pb during fetal development and early childhood. Isotope measurements (total Pb and (208)Pb/(206)Pb, (207)Pb/(206)Pb ratios) were acquired by laser ablation inductively coupled mass spectrometry at contiguous 100 micron intervals across thin sections of the teeth; from the outer enamel surface to the pulp cavity. Teeth samples (n=10) were selected from two cohorts of children, aged 5-8 years, living in NE England. By integrating the isotope data with histological analysis of the teeth, using the daily incremental lines in dentine, we were able to assign true estimated ages to each ablation point (first 2-3 years for molars, first 1-2 years for incisors+pre-natal growth). Significant differences were observed in the isotope composition and concentration of Pb between children, reflecting differences in the timing and sources of exposure during early childhood. Those born in 2000, after the withdrawal of leaded petrol in 1999, have the lowest dentine Pb levels (<0.2µgPb/g) with (208)Pb/(206)Pb (mean ±2σ: 2.126-2.079) (208)Pb/(206)Pb (mean ±2σ: 0.879-0.856) ratios that correlate very closely with modern day Western European industrial aerosols (PM10, PM2.5) suggesting that diffuse airborne pollution was probably the primary source and exposure pathway. Legacy lead, if present, is insignificant. For those born in 1997, dentine lead levels are typically higher (>0.4µgPb/g) with (208)Pb/(206)Pb (mean ±2σ: 2.145-2.117) (208)Pb/(206)Pb (mean ±2σ: 0.898-0.882) ratios that can be modelled as a binary mix between industrial aerosols and leaded petrol emissions. Short duration, high intensity exposure events (1-2 months) were readily identified, together with evidence that dentine provides a good proxy for childhood changes in the isotope composition of blood Pb. Our pilot study confirms that

  12. An application of nitrogen microwave-induced plasma mass spectrometry to isotope dilution analysis of selenium in marine organisms.

    PubMed

    Shirasaki, T; Yoshinaga, J; Morita, M; Okumoto, T; Oishi, K

    1996-01-01

    Nitrogen microwave-induced plasma mass spectrometry was studied for its applicability to the isotope dilution analysis of selenium in biological samples. Spectroscopic interference by calcium, which is present in high concentrations in biological samples, was investigated. No detectable background spectrum was observed for the major selenium isotopes of 78Se and 80Se. No detectable interferences by sodium, potassium, calcium and phosphorus on the isotope ratio 80Se/78Se were observed up to concentration of 200 mg/ml. The method was applied to the analysis of selenium in biological reference materials of marine organisms. The results showed good agreement between the certified and found values. PMID:8848792

  13. Development and experimental verification of a finite element method for accurate analysis of a surface acoustic wave device

    NASA Astrophysics Data System (ADS)

    Mohibul Kabir, K. M.; Matthews, Glenn I.; Sabri, Ylias M.; Russo, Salvy P.; Ippolito, Samuel J.; Bhargava, Suresh K.

    2016-03-01

    Accurate analysis of surface acoustic wave (SAW) devices is highly important due to their use in ever-growing applications in electronics, telecommunication and chemical sensing. In this study, a novel approach for analyzing the SAW devices was developed based on a series of two-dimensional finite element method (FEM) simulations, which has been experimentally verified. It was found that the frequency response of the two SAW device structures, each having slightly different bandwidth and center lobe characteristics, can be successfully obtained utilizing the current density of the electrodes via FEM simulations. The two SAW structures were based on XY Lithium Niobate (LiNbO3) substrates and had two and four electrode finger pairs in both of their interdigital transducers, respectively. Later, SAW devices were fabricated in accordance with the simulated models and their measured frequency responses were found to correlate well with the obtained simulations results. The results indicated that better match between calculated and measured frequency response can be obtained when one of the input electrode finger pairs was set at zero volts and all the current density components were taken into account when calculating the frequency response of the simulated SAW device structures.

  14. Analysis and accurate reconstruction of incomplete data in X-ray differential phase-contrast computed tomography.

    PubMed

    Fu, Jian; Tan, Renbo; Chen, Liyuan

    2014-01-01

    X-ray differential phase-contrast computed tomography (DPC-CT) is a powerful physical and biochemical analysis tool. In practical applications, there are often challenges for DPC-CT due to insufficient data caused by few-view, bad or missing detector channels, or limited scanning angular range. They occur quite frequently because of experimental constraints from imaging hardware, scanning geometry, and the exposure dose delivered to living specimens. In this work, we analyze the influence of incomplete data on DPC-CT image reconstruction. Then, a reconstruction method is developed and investigated for incomplete data DPC-CT. It is based on an algebraic iteration reconstruction technique, which minimizes the image total variation and permits accurate tomographic imaging with less data. This work comprises a numerical study of the method and its experimental verification using a dataset measured at the W2 beamline of the storage ring DORIS III equipped with a Talbot-Lau interferometer. The numerical and experimental results demonstrate that the presented method can handle incomplete data. It will be of interest for a wide range of DPC-CT applications in medicine, biology, and nondestructive testing.

  15. An evaluation, comparison, and accurate benchmarking of several publicly available MS/MS search algorithms: sensitivity and specificity analysis.

    PubMed

    Kapp, Eugene A; Schütz, Frédéric; Connolly, Lisa M; Chakel, John A; Meza, Jose E; Miller, Christine A; Fenyo, David; Eng, Jimmy K; Adkins, Joshua N; Omenn, Gilbert S; Simpson, Richard J

    2005-08-01

    MS/MS and associated database search algorithms are essential proteomic tools for identifying peptides. Due to their widespread use, it is now time to perform a systematic analysis of the various algorithms currently in use. Using blood specimens used in the HUPO Plasma Proteome Project, we have evaluated five search algorithms with respect to their sensitivity and specificity, and have also accurately benchmarked them based on specified false-positive (FP) rates. Spectrum Mill and SEQUEST performed well in terms of sensitivity, but were inferior to MASCOT, X!Tandem, and Sonar in terms of specificity. Overall, MASCOT, a probabilistic search algorithm, correctly identified most peptides based on a specified FP rate. The rescoring algorithm, PeptideProphet, enhanced the overall performance of the SEQUEST algorithm, as well as provided predictable FP error rates. Ideally, score thresholds should be calculated for each peptide spectrum or minimally, derived from a reversed-sequence search as demonstrated in this study based on a validated data set. The availability of open-source search algorithms, such as X!Tandem, makes it feasible to further improve the validation process (manual or automatic) on the basis of "consensus scoring", i.e., the use of multiple (at least two) search algorithms to reduce the number of FPs. complement.

  16. An evaluation, comparison, and accurate benchmarking of several publicly available MS/MS search algorithms: Sensitivity and Specificity analysis.

    SciTech Connect

    Kapp, Eugene; Schutz, Frederick; Connolly, Lisa M.; Chakel, John A.; Meza, Jose E.; Miller, Christine A.; Fenyo, David; Eng, Jimmy K.; Adkins, Joshua N.; Omenn, Gilbert; Simpson, Richard

    2005-08-01

    MS/MS and associated database search algorithms are essential proteomic tools for identifying peptides. Due to their widespread use, it is now time to perform a systematic analysis of the various algorithms currently in use. Using blood specimens used in the HUPO Plasma Proteome Project, we have evaluated five search algorithms with respect to their sensitivity and specificity, and have also accurately benchmarked them based on specified false-positive (FP) rates. Spectrum Mill and SEQUEST performed well in terms of sensitivity, but were inferior to MASCOT, X-Tandem, and Sonar in terms of specificity. Overall, MASCOT, a probabilistic search algorithm, correctly identified most peptides based on a specified FP rate. The rescoring algorithm, Peptide Prophet, enhanced the overall performance of the SEQUEST algorithm, as well as provided predictable FP error rates. Ideally, score thresholds should be calculated for each peptide spectrum or minimally, derived from a reversed-sequence search as demonstrated in this study based on a validated data set. The availability of open-source search algorithms, such as X-Tandem, makes it feasible to further improve the validation process (manual or automatic) on the basis of ''consensus scoring'', i.e., the use of multiple (at least two) search algorithms to reduce the number of FPs. complement.

  17. Mathematical analysis and algorithms for efficiently and accurately implementing stochastic simulations of short-term synaptic depression and facilitation.

    PubMed

    McDonnell, Mark D; Mohan, Ashutosh; Stricker, Christian

    2013-01-01

    The release of neurotransmitter vesicles after arrival of a pre-synaptic action potential (AP) at cortical synapses is known to be a stochastic process, as is the availability of vesicles for release. These processes are known to also depend on the recent history of AP arrivals, and this can be described in terms of time-varying probabilities of vesicle release. Mathematical models of such synaptic dynamics frequently are based only on the mean number of vesicles released by each pre-synaptic AP, since if it is assumed there are sufficiently many vesicle sites, then variance is small. However, it has been shown recently that variance across sites can be significant for neuron and network dynamics, and this suggests the potential importance of studying short-term plasticity using simulations that do generate trial-to-trial variability. Therefore, in this paper we study several well-known conceptual models for stochastic availability and release. We state explicitly the random variables that these models describe and propose efficient algorithms for accurately implementing stochastic simulations of these random variables in software or hardware. Our results are complemented by mathematical analysis and statement of pseudo-code algorithms.

  18. Examination of the kinetic isotopic effect to the acetylation derivatization for the gas chromatographic-combustion-isotope ratio mass spectrometric doping control analysis of endogenous steroids.

    PubMed

    Angelis, Yiannis S; Kioussi, Maroula K; Kiousi, Polyxeni; Brenna, J Thomas; Georgakopoulos, Costas G

    2012-12-01

    In gas chromatographic-combustion-isotope ratio mass spectrometry (GC-C-IRMS) doping control analysis, endogenous androgenic anabolic steroids and their metabolites are commonly acetylated using acetic anhydride reagent, thus incorporating exogenous carbon that contributes to the measured isotope ratio. Comparison of the endogenous δ(13)C of free, mono-, and di-acetylated steroids requires application of corrections, typically through straightforward use of the mass balance equation. Variability in kinetic isotope effects (KIE) due to steroid structures could cause fractionation of endogenous steroid carbon, resulting in inaccurate results. To test for possible KIE influence on δ(13)C, acetic anhydride of graded isotope ratio within the natural abundance range was used under normal derivatization conditions to test for linearity. In all cases, plots of measured steroid acetate δ(13)C versus acetic anhydride δ(13)C were linear and slopes were not significantly different. Regression analysis of the Δδ(13)C of enriched acetic anhydrides versus Δδ(13)C of derivatized steroids shows that KIE are similar in all cases. We conclude that δ(13)C calculated from the mass balance equation is independent of the δ(13)C of the acetic anhydride reagent, and that net KIE under normal derivatization conditions do not bias the final reported steroid δ(13)C.

  19. Congener-specific carbon isotopic analysis of technical PCB and PCN mixtures using two-dimensional gas chromatography-isotope ratio mass spectrometry.

    PubMed

    Horii, Yuichi; Kannan, Kurunthachalam; Petrick, Gert; Gamo, Toshitaka; Falandysz, Jerzy; Yamashita, Nobuyoshi

    2005-06-01

    Analysis of stable carbon isotope fractionation is a useful method to study the sources and fate of anthropogenic organic contaminants such as polychlorinated biphenyls (PCBs) in the environment. To evaluate the utility of carbon isotopes, determination of isotopic ratios of 13C/12C in source materials, for example, technical PCB preparations, is needed. In this study, we determined delta13C values of 31 chlorobiphenyl (CB) congeners in 18 technical PCB preparations and 15 chloronaphthalene (CN) congeners in 6 polychlorinated naphthalene preparations using two-dimensional gas chromatography-combustion furnace-isotope ratio mass spectrometry (2DGC-C-IRMS). Development of 2DGC-IRMS enabled improved resolution and sensitivity of compound-specific carbon isotope analysis (CSIA) of CB or CN congeners. Delta13C values of PCB congeners ranged from -34.4 (Delors) to -22.0/1000 (Sovol). Analogous PCB preparations with similar chlorine content, but different geographical origin, had different delta13C values. PCB preparations from Eastern European countries--Delors, Sovol, Trichlorodiphenyl, and Chlorofen--had distinct delta13C values. PCB mixtures showed increased 13C depletion with increasing chlorine content. Delta13C values for individual CB congeners varied depending on the degree of chlorination in technical mixtures. Delta13C values of CN congeners in Halowaxes ranged from -26.3 to -21.7/1000 and these values are within the ranges observed for PCBs. This study establishes the range of delta13C values in technical PCB and PCN preparations, which may prove to be useful in the determination of sources of these compounds in the environment. This is the first study to employ 2DGC-IRMS analysis of delta13C values in technical PCB and PCN preparations.

  20. Technical Note: A simple method for vaterite precipitation for isotopic studies: implications for bulk and clumped isotope analysis

    NASA Astrophysics Data System (ADS)

    Kluge, T.; John, C. M.

    2015-06-01

    Calcium carbonate (CaCO3) plays an important role in the natural environment as a major constituent of the skeleton and supporting structure of marine life and has high economic importance as an additive in food, chemicals and medical products. Anhydrous CaCO3 occurs in the three different polymorphs calcite, aragonite and vaterite, whereof calcite is the most abundant and best characterized mineral. In contrast, little is known about the rare polymorph vaterite, in particular with regard to the oxygen isotope fractionation between H2O and the mineral. Synthetic precipitation of vaterite in the laboratory typically involves rapid processes and isotopic non-equilibrium, which excludes isotope studies focused on the characterization of vaterite under equilibrium conditions. Here, we used a new experimental approach that enables vaterite mineral formation from an isotopically equilibrated solution. The solution consists of a ~0.007 mol L-1 CaCO3 solution that is saturated with NaCl at room temperature (up to 6.4 mol L-1). Vaterite precipitated as single phase or major phase (≥94%) in experiments performed between 23 and 91 °C. Only at 80 °C was vaterite a minor phase with a relative abundance of 27%. The high mineral yield per experiment of up to 235 mg relative to the initially dissolved CaCO3 amount of on average 360 mg enables an investigation of the oxygen isotope fractionation between the mineral and water, and the determination of clumped isotope values in vaterite.

  1. Automated CO2 extraction from air for clumped isotope analysis in the atmo- and biosphere

    NASA Astrophysics Data System (ADS)

    Hofmann, Magdalena; Ziegler, Martin; Pons, Thijs; Lourens, Lucas; Röckmann, Thomas

    2015-04-01

    The conventional stable isotope ratios 13C/12C and 18O/16O in atmospheric CO2 are a powerful tool for unraveling the global carbon cycle. In recent years, it has been suggested that the abundance of the very rare isotopologue 13C18O16O on m/z 47 might be a promising tracer to complement conventional stable isotope analysis of atmospheric CO2 [Affek and Eiler, 2006; Affek et al. 2007; Eiler and Schauble, 2004; Yeung et al., 2009]. Here we present an automated analytical system that is designed for clumped isotope analysis of atmo- and biospheric CO2. The carbon dioxide gas is quantitatively extracted from about 1.5L of air (ATP). The automated stainless steel extraction and purification line consists of three main components: (i) a drying unit (a magnesium perchlorate unit and a cryogenic water trap), (ii) two CO2 traps cooled with liquid nitrogen [Werner et al., 2001] and (iii) a GC column packed with Porapak Q that can be cooled with liquid nitrogen to -30°C during purification and heated up to 230°C in-between two extraction runs. After CO2 extraction and purification, the CO2 is automatically transferred to the mass spectrometer. Mass spectrometric analysis of the 13C18O16O abundance is carried out in dual inlet mode on a MAT 253 mass spectrometer. Each analysis generally consists of 80 change-over-cycles. Three additional Faraday cups were added to the mass spectrometer for simultaneous analysis of the mass-to-charge ratios 44, 45, 46, 47, 48 and 49. The reproducibility for δ13C, δ18O and Δ47 for repeated CO2 extractions from air is in the range of 0.11o (SD), 0.18o (SD) and 0.02 (SD)o respectively. This automated CO2 extraction and purification system will be used to analyse the clumped isotopic signature in atmospheric CO2 (tall tower, Cabauw, Netherlands) and to study the clumped isotopic fractionation during photosynthesis (leaf chamber experiments) and soil respiration. References Affek, H. P., Xu, X. & Eiler, J. M., Geochim. Cosmochim. Acta 71, 5033

  2. Biomedical and Forensic Applications of Combined Catalytic Hydrogenation-Stable Isotope Ratio Analysis

    PubMed Central

    Sephton, Mark A.; Meredith, Will; Sun, Cheng-Gong; Snape, Colin E.

    2007-01-01

    Studies of biological molecules such as fatty acids and the steroid hormones have the potential to benefit enormously from stable carbon isotope ratio measurements of individual molecules. In their natural form, however, the body’s molecules interact too readily with laboratory equipment designed to separate them for accurate measurements to be made. Some methods overcome this problem by adding carbon to the target molecule, but this can irreversibly overprint the carbon source ‘signal’. Hydropyrolysis is a newly-applied catalytic technique that delicately strips molecules of their functional groups but retains their carbon skeletons and stereochemistries intact, allowing precise determination of the carbon source. By solving analytical problems, the new technique is increasing the ability of scientists to pinpoint molecular indicators of disease, elucidate metabolic pathways and recognise administered substances in forensic investigations. PMID:19662175

  3. Recent developments in stable isotope dilution assays in mycotoxin analysis with special regard to Alternaria toxins.

    PubMed

    Asam, Stefan; Rychlik, Michael

    2015-10-01

    Stable isotope dilution assays (SIDAs) are becoming ever commoner in mycotoxin analysis, and the number of synthesized or commercially available isotopically labelled compounds has greatly increased in the 7 years since our last review dealing with this topic. Thus, this review is conceived as an update for new applications or improvements of SIDAs for compounds discussed earlier, but the main focus is on newly introduced labelled substances and the development of SIDAs for, for example, fusarin C, moniliformin or the enniatins. Mycotoxin research has concentrated on the emerging group of Alternaria toxins in recent years, and a series of SIDAs have been developed, including ones for tenuazonic acid, alternariol, altertoxins and tentoxin that are discussed in detail in this review. Information about synthetic routes, isotopic purity and mass-spectrometric characterization of labelled compounds is given, as well as about the development and validation of SIDAs and their application to foods, feeds or biological samples. As the number of commercially available labelled standards is increasing continuously, a general tendency for the use of analytical methods based on liquid chromatography coupled with mass spectrometry capable of identifying a series of mycotoxins simultaneously ("multimethods") and using one or more labelled internal standards can be observed. An overview of these applications is given, thus demonstrating that SIDAs are increasingly being used in routine analysis.

  4. A rapid method for the sampling of atmospheric water vapour for isotopic analysis.

    PubMed

    Peters, Leon I; Yakir, Dan

    2010-01-01

    Analysis of the stable isotopic composition of atmospheric moisture is widely applied in the environmental sciences. Traditional methods for obtaining isotopic compositional data from ambient moisture have required complicated sampling procedures, expensive and sophisticated distillation lines, hazardous consumables, and lengthy treatments prior to analysis. Newer laser-based techniques are expensive and usually not suitable for large-scale field campaigns, especially in cases where access to mains power is not feasible or high spatial coverage is required. Here we outline the construction and usage of a novel vapour-sampling system based on a battery-operated Stirling cycle cooler, which is simple to operate, does not require any consumables, or post-collection distillation, and is light-weight and highly portable. We demonstrate the ability of this system to reproduce delta(18)O isotopic compositions of ambient water vapour, with samples taken simultaneously by a traditional cryogenic collection technique. Samples were collected over 1 h directly into autosampler vials and were analysed by mass spectrometry after pyrolysis of 1 microL aliquots to CO. This yielded an average error of < +/-0.5 per thousand, approximately equal to the signal-to-noise ratio of traditional approaches. This new system provides a rapid and reliable alternative to conventional cryogenic techniques, particularly in cases requiring high sample throughput or where access to distillation lines, slurry maintenance or mains power is not feasible. PMID:19960497

  5. Diffusion sampler for compound specific carbon isotope analysis of dissolved hydrocarbon contaminants.

    PubMed

    Passeport, Elodie; Landis, Richard; Mundle, Scott O C; Chu, Katrina; Mack, E Erin; Lutz, Edward; Lollar, Barbara Sherwood

    2014-08-19

    Compound Specific Isotope Analysis (CSIA) is widely utilized to study the fate of organic contaminants in groundwater. To date, however, no method is available to obtain CSIA samples at a fine (cm) spatial scale across the sediment-surface water interface (SWI), a key boundary for discharge of contaminated groundwater to surface water. Dissolved contaminants in such discharged zones undergo rapid temporal and spatial changes due to heterogeneity in redox conditions and microbial populations. The compatibility of a passive sediment pore water sampler ("peeper") to collect 40 mL samples for CSIA of benzene, toluene, monochlorobenzene, and 1,2-dichlorobenzene at field-relevant concentrations (0.1-5 mg L(-1)) was evaluated in laboratory experiments. Results demonstrate that physical diffusion across the polysulfone membrane does not alter the carbon isotope values (±0.5‰). Measured δ(13)C values also remain invariant despite significant adsorption of the compounds on the peeper material, an effect which increased with higher numbers of chlorine atoms and sorption coefficient (Koc) values. In addition, isotope equilibrium between the peeper chamber and the sediment pore water occurred in less than a day, indicating the peeper method can be used to provide samples for CSIA analysis at fine spatial and temporal sampling resolutions in contaminated sediments. PMID:25058598

  6. Compound-specific carbon isotope analysis of a contaminant plume in Kingsford, Michigan, USA

    USGS Publications Warehouse

    Michel, R.L.; Silva, S.R.; Bemis, B.; Godsy, E.M.; Warren, E.

    2001-01-01

    Compound-specific isotope analysis was used to study a contaminated site near Kingsford, Michigan, USA. Organic compounds at three of the sites studied had similar ??13C values indicating that the contaminant source is the same for all sites. At a fourth site, chemical and ??13C values had evolved due to microbial degradation of organics, with the ??13C being much heavier than the starting materials. A microcosm experiment was run to observe isotopic changes with time in the methane evolved and in compounds remaining in the water during degradation. The ??13C values of the methane became heavier during the initial period of the run when volatile fatty acids were being consumed. There was an abrupt decrease in the ??13C values when fatty acids had been consumed and phenols began to be utilized. The ??13C value of the propionate remaining in solution also increased, similar to the results found in the field.

  7. INTERACTION BETWEEN INLAND AND SEA THROUGH RAUSU RIVER USING ISOTOPE ANALYSIS

    NASA Astrophysics Data System (ADS)

    Aynur, Abliz; Nakayama, Keisuke; Maruya, Yasuyuki; Kuwae, Tomohiro; Okada, Tomonari; Ishida, Tetsuya

    The Shiretoko is a pennusla where a unique interaction occurs between the terrestrial and oceanic systems, which are linked by nutrient exchange processes. Nutrient rich floating sea ice is transported to the coast from the Okhotsk Sea and salmon and trout move upstream and feed inland animals, such as bears and birds. Conversely, nutrients flow into the ocean through rivers. It has been reported that this unique nutrient circulation is being disrupted by climate change and it is thus important to understand what mechanisms drive nutrient circulation in Shiretoko and maintain a unique ecological system. In this study, stable isotope analysis is used in combination to determine the contribution of land-derived (LDN) and marine-derived nutrients (MDN) in the Rausu River basin. Stable isotopes ratios, δ13C and δ15N, show a higher contribution of MDN before the snow-melt floods, and that MDN are distributed largely in the downstream region of the basin.

  8. A New, Rapid, Precise and Sensitive Method for Chlorine Stable Isotope Analysis of Chlorinated Aliphatic Hydrocarbons

    NASA Astrophysics Data System (ADS)

    van Acker, M. R.; Shahar, A.; Young, E. D.; Coleman, M. L.

    2005-12-01

    Chlorinated aliphatic hydrocarbons (CAH) are recognized common groundwater contaminants. Because of their physico-chemical properties, their lifespan in groundwater is in the order of decades (Pankow and Cherry, 1996). Stable isotopes can play a role in determining the rate and extent of CAH attenuation (Slater, 2003). The use of chlorine has been hampered by the current time consuming and insensitive analytical methods. We present a new analytical procedure to measure chlorine stable isotope values using a gas chromatograph coupled to a multi-collector inductively coupled mass spectrometer (GC-MC-ICP-MS). The GC has a Porapack Q packed column. The carrier gas was helium and the temperature was constant at 160°C. The GC was coupled to the MC-ICP-MS by heated stainless steel tubing. Our high resolution spectra showed that 37Cl is free of its main interference 36Ar-H over a range of 0.004 amu. Two pure CAH, trichloroethene (TCE) and tetrachloroethene (PCE), were used for zero enrichment (sample relative to itself) and standard-sample difference measurements. Integrations and background corrections of transient signals were performed using Microsoft Excel after import of the raw data from the MC-ICPMS acquisition software. Zero enrichment tests with TCE and PCE yielded δ37Cl of -0.04±0.16‰ and -0.03±0.17‰, respectively, results for sample injections of 0.12 to 0.02 microliters. Accuracy was tested by injecting 0.24 microliters of a 50/50 mixture of TCE and PCE of known isotopic compositions as the difference between the two solvents was of paramount interest. The δ37Cl(TCE) value of PCE was -1.99±0.16‰. A highly satisfactory comparison with the conventional method is shown by published values for TCE and PCE, -2.04±0.12‰ and -0.30±0.14‰, respectively (Jendrzejewski et al., 2001), giving a δ37Cl(TCE) value for PCE of -2.34±0.18‰. These tests of the GC-MC-ICP-MS method showed that we can obtain reproducible and accurate Cl isotope values using an

  9. Stable-isotope dilution LC–MS for quantitative biomarker analysis

    PubMed Central

    Ciccimaro, Eugene; Blair, Ian A

    2010-01-01

    The ability to conduct validated analyses of biomarkers is critically important in order to establish the sensitivity and selectivity of the biomarker in identifying a particular disease. The use of stable-isotope dilution (SID) methodology in combination with LC–MS/MS provides the highest possible analytical specificity for quantitative determinations. This methodology is now widely used in the discovery and validation of putative exposure and disease biomarkers. This review will describe the application of SID LC–MS methodology for the analysis of small-molecule and protein biomarkers. It will also discuss potential future directions for the use of this methodology for rigorous biomarker analysis. PMID:20352077

  10. Copper and tin isotopic analysis of ancient bronzes for archaeological investigation: development and validation of a suitable analytical methodology.

    PubMed

    Balliana, Eleonora; Aramendía, Maite; Resano, Martin; Barbante, Carlo; Vanhaecke, Frank

    2013-03-01

    Although in many cases Pb isotopic analysis can be relied on for provenance determination of ancient bronzes, sometimes the use of "non-traditional" isotopic systems, such as those of Cu and Sn, is required. The work reported on in this paper aimed at revising the methodology for Cu and Sn isotope ratio measurements in archaeological bronzes via optimization of the analytical procedures in terms of sample pre-treatment, measurement protocol, precision, and analytical uncertainty. For Cu isotopic analysis, both Zn and Ni were investigated for their merit as internal standard (IS) relied on for mass bias correction. The use of Ni as IS seems to be the most robust approach as Ni is less prone to contamination, has a lower abundance in bronzes and an ionization potential similar to that of Cu, and provides slightly better reproducibility values when applied to NIST SRM 976 Cu isotopic reference material. The possibility of carrying out direct isotopic analysis without prior Cu isolation (with AG-MP-1 anion exchange resin) was investigated by analysis of CRM IARM 91D bronze reference material, synthetic solutions, and archaeological bronzes. Both procedures (Cu isolation/no Cu isolation) provide similar δ (65)Cu results with similar uncertainty budgets in all cases (±0.02-0.04 per mil in delta units, k = 2, n = 4). Direct isotopic analysis of Cu therefore seems feasible, without evidence of spectral interference or matrix-induced effect on the extent of mass bias. For Sn, a separation protocol relying on TRU-Spec anion exchange resin was optimized, providing a recovery close to 100 % without on-column fractionation. Cu was recovered quantitatively together with the bronze matrix with this isolation protocol. Isotopic analysis of this Cu fraction provides δ (65)Cu results similar to those obtained upon isolation using AG-MP-1 resin. This means that Cu and Sn isotopic analysis of bronze alloys can therefore be carried out after a single chromatographic

  11. In situ SIMS oxygen isotope analysis of olivine in the Tibetan mantle xenoliths

    NASA Astrophysics Data System (ADS)

    Zhao, Zhidan; Zhu, Di-Cheng; Liu, Dong; Mo, Xuanxue

    2016-04-01

    Although the mantle-derived xenoliths from Lhasa terrane provide a means of directly investigating the mantle underlying the southern part of the plateau, they were rarely found in the region. The only case of mantle xenoliths came from the Sailipu ultrapotassic volcanic rocks, erupted at ˜17 Ma, which have indicated that the subcontinental mantle of southern Tibetan Plateau is hot and strongly influenced by metasomatism (Zhao et al., 2008a, b; Liu et al., 2011). A further study by Liu et al.(2014) of in-situ oxygen isotope of olivine crystals in Sailipu mantle xenoliths identify a metasomatized mantle reservoir that interpreted as the sub-arc lithospheric mantle, with anomalously enriched oxygen isotopes (δ18O=8.03). Here we present oxygen isotopes data on the Sailipu mantle xenolith olivines, using different method of sample preparation. Mantle xenoliths (less than 1 cm in diameter) together originally with their host volcanic rocks were prepared in epoxy adjacent to grains of a San Carlos olivine intralaboratory standard and then polished to a flat and smooth surface. Oxygen isotope compositions of olivines occurs both in mantle xenolith and as phenocryst in the host rock, were analyzed in situ using CAMECA SIMS-1280 ion microprobe at the Institute of Geology and Geophysics, Chinese Academy of Sciences. We also performed traditional oxygen isotope analysis on three olivine phenocrysts separates from the host lava. Our new data show: (1) The mantle xenolith olivines have typical mantle oxygen isotopic composition (δ18O=4.8-8.0‰ with average of 5.5±0.2‰ n=105) with variety Fo#(78-90), (2) Oxygen isotopes of situ olivine phenocrysts in the Sailipu lavas (δ18O=7.1-9.2‰ Fo#=70-84, n=66), are similar to that of the whole rock (δ18O=7.0-9.4‰ Fo#=64-74, n=8, Zhao et al., 2009), and three olivine phenocryst grains (δ18O=7.2-7.8); (3) The intralaboratory standard of San Carlos olivine can be a suitable standard using for analyzing olivines with Fo not only

  12. Detection of Human Sewage in Urban Stormwater Using DNA Based Methods and Stable Isotope Analysis

    NASA Astrophysics Data System (ADS)

    McLellan, S. L.; Malet, N.; Sauer, E.; Mueller-Spitz, S.; Borchardt, M.

    2008-12-01

    related to the mixed organic matter sources in polluted stormwater runoff, and that this signal will distinct from untreated sanitary sewage. Stable isotope signatures of stormwater and untreated sewage were determined and compared with the rivers. Isotopic values of stormwater was delta 15N = 1.1 ± 2 %; delta 13C = -25.5 ± 3 % and sewage was delta 15N = -1.9 ± 0.2 %; delta 13C = -23.6 ± 0.3. Suspended particular organic matter (SPOM) of Milwaukee River showed depleted delta 13C (-28.6 ± 1.6 %) and enriched delta 15N (7.7 ± 1.9 %) values. SPOM of the KK River exhibited the most depleted delta 15N (0.2 ± 1.6 %) and enriched delta 13C (-24.8 ± 1.8 %) isotopic values. Menomonee River SPOM showed intermediate isotopic values. The delta 13C values of each river and the estuary enriched significantly throughout the summer storm periods. The isotope signals in the KK and Menomonee were indicative of stormwater runoff and sewage contamination. These results suggest that unrecognized sewage inputs are chronically present and may be delivered through urban stormwater systems. DNA based methods combined with isotope analysis may provide a useful tool for urban watershed assessments and to identify sewage inputs. Delineating the relative contribution of stormwater and sewage to overall degraded water quality might give the first indication of the impact of these sources on the Michigan Lake waters.

  13. Matrix Effects on the MC-ICPMS Analysis of Zn and Cd Isotopes

    NASA Astrophysics Data System (ADS)

    Shiel, A. E.; Weis, D.; Barling, J.; Orians, K. J.

    2006-12-01

    In order to understand fractionation in heavy stable isotope systems, matrix and auto-matrix effects need to be carefully monitored as they have a major impact on the precision and accuracy of isotope measurement by MC-ICP-MS. Understanding their impact for any given isotopic system is an important aspect of method development. In this study we look at auto-matrix and matrix effects for Zn (Cu mass bias correction) and Cd (Ag mass bias correction). Zn and Cd have similarly high ionization potentials, 9.4 and 9.0 respectively, and ionization potentials for Cu and Ag are similar, 7.7 and 7.6 respectively, making for an interesting comparison. All experiments were performed on a Nu Plasma MC-ICP-MS with 5x molar concentration of matrix elements. Experiments were also performed at concentrations more representative of those likely to be found in purified samples. In addition, we tested auto-matrix effects for Cd and Zn by varying the concentration of the analyte and mass bias correcting element. Cd sensitivity is enhanced in the presence of Rb and Pb, and is suppressed in the presence of Al, Sr and Cs. Spiked Cd runs are isotopically lighter than un-spiked runs, as light as 0.4‰/amu. Ag sensitivity was enhanced by all matrix elements. Cu sensitivity is enhanced by Al, Sr and Ba, and Zn sensitivity is enhanced by the latter two and Pb. Zn spiked with Al, Sr and Pb, or with poorly matched Cu intensities is isotopically lighter than un-spiked standards, as light as 1.0‰/amu. Auto-matrix effects for Cd and Ag, if present, are within the analytical error. We demonstrate that the presence of matrix elements or differences in concentration of analyte and mass bias correcting element between sample and standard can produce fractionation that is not true. The matrix effect is also found to be variable, as replicate analyses do not always agree. Cd and Zn react differently to different matrix elements, demonstrating the need for independent evaluation of each isotopic system

  14. Molecular-genetic analysis is essential for accurate classification of renal carcinoma resembling Xp11.2 translocation carcinoma.

    PubMed

    Hayes, Malcolm; Peckova, Kvetoslava; Martinek, Petr; Hora, Milan; Kalusova, Kristyna; Straka, Lubomir; Daum, Ondrej; Kokoskova, Bohuslava; Rotterova, Pavla; Pivovarčikova, Kristyna; Branzovsky, Jindrich; Dubova, Magdalena; Vesela, Pavla; Michal, Michal; Hes, Ondrej

    2015-03-01

    tumours can only be sub-classified accurately by multi-parameter molecular-genetic analysis. PMID:25544614

  15. Stable isotope analysis of vertebrae reveals ontogenetic changes in habitat in an endothermic pelagic shark.

    PubMed

    Carlisle, Aaron B; Goldman, Kenneth J; Litvin, Steven Y; Madigan, Daniel J; Bigman, Jennifer S; Swithenbank, Alan M; Kline, Thomas C; Block, Barbara A

    2015-01-22

    Ontogenetic changes in habitat are driven by shifting life-history requirements and play an important role in population dynamics. However, large portions of the life history of many pelagic species are still poorly understood or unknown. We used a novel combination of stable isotope analysis of vertebral annuli, Bayesian mixing models, isoscapes and electronic tag data to reconstruct ontogenetic patterns of habitat and resource use in a pelagic apex predator, the salmon shark (Lamna ditropis). Results identified the North Pacific Transition Zone as the major nursery area for salmon sharks and revealed an ontogenetic shift around the age of maturity from oceanic to increased use of neritic habitats. The nursery habitat may reflect trade-offs between prey availability, predation pressure and thermal constraints on juvenile endothermic sharks. The ontogenetic shift in habitat coincided with a reduction of isotopic niche, possibly reflecting specialization upon particular prey or habitats. Using tagging data to inform Bayesian isotopic mixing models revealed that adult sharks primarily use neritic habitats of Alaska yet receive a trophic subsidy from oceanic habitats. Integrating the multiple methods used here provides a powerful approach to retrospectively study the ecology and life history of migratory species throughout their ontogeny.

  16. Stable isotope analysis of 1987-1991 zooplankton samples and bowhead whale tissues. Final report

    SciTech Connect

    Schell, D.M.

    1992-06-01

    Stable isotope analyses of bowhead whale tissue samples and bowhead whale prey organisms collected over the years 1987 to 1991 were used to provide detail on the isotope ratio gradients evident in the arctic Alaskan zooplankton and to verify previous findings regarding the growth rates and age determination techniques developed for bowhead whales. Zooplankton of the Bering and Chukchi seas are enriched in (13)C relative to the eastern Beaufort Sea. The analysis of baleen from bowhead whales taken between 1987 to 1990 indicate that the whales are slow-growing and the young animals between year one and about six to seven years of age, undergo a period of little or no linear growth. The authors estimate that bowheads require 16-18 years to reach the length of sexual maturity, i.e., 13-14 m. From baleen Delta(13C) cycles, a 20 year record of the isotope ratios in the phytoplankton of the northern Bering and Chukchi seas was constructed. The long-term record has been compared with the temperature anomalies in surface waters of the Bering Sea. The Delta(13C) of the zooplankton is inversely correlated with temperature and refutes current models attempting to relate ocean temperature, and atmospheric carbon dioxide levels with the Delta(13C) of ocean sediment organic matter.

  17. Stable isotope analysis of vertebrae reveals ontogenetic changes in habitat in an endothermic pelagic shark

    PubMed Central

    Carlisle, Aaron B.; Goldman, Kenneth J.; Litvin, Steven Y.; Madigan, Daniel J.; Bigman, Jennifer S.; Swithenbank, Alan M.; Kline, Thomas C.; Block, Barbara A.

    2015-01-01

    Ontogenetic changes in habitat are driven by shifting life-history requirements and play an important role in population dynamics. However, large portions of the life history of many pelagic species are still poorly understood or unknown. We used a novel combination of stable isotope analysis of vertebral annuli, Bayesian mixing models, isoscapes and electronic tag data to reconstruct ontogenetic patterns of habitat and resource use in a pelagic apex predator, the salmon shark (Lamna ditropis). Results identified the North Pacific Transition Zone as the major nursery area for salmon sharks and revealed an ontogenetic shift around the age of maturity from oceanic to increased use of neritic habitats. The nursery habitat may reflect trade-offs between prey availability, predation pressure and thermal constraints on juvenile endothermic sharks. The ontogenetic shift in habitat coincided with a reduction of isotopic niche, possibly reflecting specialization upon particular prey or habitats. Using tagging data to inform Bayesian isotopic mixing models revealed that adult sharks primarily use neritic habitats of Alaska yet receive a trophic subsidy from oceanic habitats. Integrating the multiple methods used here provides a powerful approach to retrospectively study the ecology and life history of migratory species throughout their ontogeny. PMID:25621332

  18. Stable isotope analysis of vertebrae reveals ontogenetic changes in habitat in an endothermic pelagic shark.

    PubMed

    Carlisle, Aaron B; Goldman, Kenneth J; Litvin, Steven Y; Madigan, Daniel J; Bigman, Jennifer S; Swithenbank, Alan M; Kline, Thomas C; Block, Barbara A

    2015-01-22

    Ontogenetic changes in habitat are driven by shifting life-history requirements and play an important role in population dynamics. However, large portions of the life history of many pelagic species are still poorly understood or unknown. We used a novel combination of stable isotope analysis of vertebral annuli, Bayesian mixing models, isoscapes and electronic tag data to reconstruct ontogenetic patterns of habitat and resource use in a pelagic apex predator, the salmon shark (Lamna ditropis). Results identified the North Pacific Transition Zone as the major nursery area for salmon sharks and revealed an ontogenetic shift around the age of maturity from oceanic to increased use of neritic habitats. The nursery habitat may reflect trade-offs between prey availability, predation pressure and thermal constraints on juvenile endothermic sharks. The ontogenetic shift in habitat coincided with a reduction of isotopic niche, possibly reflecting specialization upon particular prey or habitats. Using tagging data to inform Bayesian isotopic mixing models revealed that adult sharks primarily use neritic habitats of Alaska yet receive a trophic subsidy from oceanic habitats. Integrating the multiple methods used here provides a powerful approach to retrospectively study the ecology and life history of migratory species throughout their ontogeny. PMID:25621332

  19. An approach for assessing total instrumental uncertainty in compound-specific carbon isotope analysis: implications for environmental remediation studies.

    PubMed

    Lollar, Barbara Sherwood; Hirschorn, Sarah K; Chartrand, Michelle M G; Lacrampe-Couloume, Georges

    2007-05-01

    Determination of compound-specific carbon isotope values by continuous flow isotope ratio mass spectrometry is impacted by variation in several routine operating parameters of which one of the most important is signal size, or linearity. Experiments were carried out to evaluate the implications of these operating parameters on both reproducibility and accuracy of delta13C measurements. A new method is described for assessing total instrumental uncertainty of routine compound-specific delta13C analysis, incorporating both accuracy and reproducibility. These findings have important implications for application of compound-specific isotope analysis in environmental geochemistry and in particular for the rapidly developing field of isotopic investigation of biodegradation and remediation of organic chemicals in contaminant hydrogeology. PMID:17391005

  20. An approach for assessing total instrumental uncertainty in compound-specific carbon isotope analysis: implications for environmental remediation studies.

    PubMed

    Lollar, Barbara Sherwood; Hirschorn, Sarah K; Chartrand, Michelle M G; Lacrampe-Couloume, Georges

    2007-05-01

    Determination of compound-specific carbon isotope values by continuous flow isotope ratio mass spectrometry is impacted by variation in several routine operating parameters of which one of the most important is signal size, or linearity. Experiments were carried out to evaluate the implications of these operating parameters on both reproducibility and accuracy of delta13C measurements. A new method is described for assessing total instrumental uncertainty of routine compound-specific delta13C analysis, incorporating both accuracy and reproducibility. These findings have important implications for application of compound-specific isotope analysis in environmental geochemistry and in particular for the rapidly developing field of isotopic investigation of biodegradation and remediation of organic chemicals in contaminant hydrogeology.

  1. High Precision Fe Isotope Analysis in low Concentration Samples by High Resolution MC-ICPMS

    NASA Astrophysics Data System (ADS)

    Chung, C.; Wu, J.; You, C.

    2009-12-01

    Iron availability has been shown to be the main limitation factor for phytoplankton growth in the ocean. However, due to the limitation of analytical technique, the database of dissolved Fe concentrations and isotope ratio distribution in the ocean is still very limited. In particular, the iron sources to the ocean remain uncertain. Aeolian dust from the continental is considered as the primary source, also the digenetic dissolution at the continental margins is proposed to contribute significant portion of iron content of the sea surface water. The field of Fe isotope geochemistry has seen important developments in methodology and scope since the advent of Multi-Collector Inductively Coupled Plasma Mass Spectrometry (MC-ICPMS). Although increasing the number of replicates in High Resolution MC-ICPMS reduces the uncertainty related to instability in instrumental mass bias and counting statistics, many other parameters include mass fractionation during column separation, matrix effect in ICPMS analysis and the presence of isobaric interferences can affect the precision and accuracy of Fe isotopic analyses. In this study, a high precision analytical method of Fe isotope measurement for low concentration samples was developed using HR-MC-ICPMS. Several parameters that may affect the accuracy and precision of 56Fe/54Fe result such as background, instrumental mass discrimination, isobaric interferences, type of introduction system and acid molarity were identified and evaluated. External precisions better than 0.04‰ for δ56Fe can be achieve using only 10ng of iron sample with APEX and X-cone as introduction system. Significant improvement in terms of sample size was made. This method can be applied on very low concentration samples such as coral and seawater.

  2. Improved method for isotopic and quantitative analysis of dissolved inorganic carbon in natural water samples.

    PubMed

    Assayag, Nelly; Rivé, Karine; Ader, Magali; Jézéquel, Didier; Agrinier, Pierre

    2006-01-01

    We present here an improved and reliable method for measuring the concentration of dissolved inorganic carbon (DIC) and its isotope composition (delta(13)C(DIC)) in natural water samples. Our apparatus, a gas chromatograph coupled to an isotope ratio mass spectrometer (GCIRMS), runs in a quasi-automated mode and is able to analyze about 50 water samples per day. The whole procedure (sample preparation, CO(2(g))-CO(2(aq)) equilibration time and GCIRMS analysis) requires 2 days. It consists of injecting an aliquot of water into a H(3)PO(4)-loaded and He-flushed 12 mL glass tube. The H(3)PO(4) reacts with the water and converts the DIC into aqueous and gaseous CO(2). After a CO(2(g))-CO(2(aq)) equilibration time of between 15 and 24 h, a portion of the headspace gas (mainly CO(2)+He) is introduced into the GCIRMS, to measure the carbon isotope ratio of the released CO(2(g)), from which the delta(13)C(DIC) is determined via a calibration procedure. For standard solutions with DIC concentrations ranging from 1 to 25 mmol . L(-1) and solution volume of 1 mL (high DIC concentration samples) or 5 mL (low DIC concentration samples), delta(13)C(DIC) values are determined with a precision (1sigma) better than 0.1 per thousand. Compared with previously published headspace equilibration methods, the major improvement presented here is the development of a calibration procedure which takes the carbon isotope fractionation associated with the CO(2(g))-CO(2(aq)) partition into account: the set of standard solutions and samples has to be prepared and analyzed with the same 'gas/liquid' and 'H(3)PO(4)/water' volume ratios. A set of natural water samples (lake, river and hydrothermal springs) was analyzed to demonstrate the utility of this new method. PMID:16810706

  3. Job/task analysis for I C (Instrumentation and Controls) instrument technicians at the High Flux Isotope Reactor

    SciTech Connect

    Duke, L.L.

    1989-09-01

    To comply with Department of Energy Order 5480.XX (Draft), a job/task analysis was initiated by the Maintenance Management Department at Oak Ridge National Laboratory (ORNL). The analysis was applicable to instrument technicians working at the ORNL High Flux Isotope Reactor (HFIR). This document presents the procedures and results of that analysis. 2 refs., 2 figs.

  4. Spatially-resolved stable isotope analysis of a hypersaline microbial mat

    NASA Astrophysics Data System (ADS)

    Moran, J.; Cory, A. B.; Lindemann, S. R.; Fredrickson, J. K.

    2012-12-01

    Hot Lake is a hypersaline, meromictic lake located in north-central Washington. High rates of evapotranspiration coupled with its location in an endorrheic basin contribute to the lake's high salinity. The predominant dissolved salt is magnesium sulfate; hypolimnion waters may seasonally exceed 2 M magnesium sulfate concentrations. In addition to extreme salinity, horizons within the lake seasonally exceed 50 °C, in part due to the enhanced light absorption by magnesium sulfate-saturated water. Despite extreme and highly variable seasonal conditions (salinity, temperature, photon flux), dense benthic microbial mats composed of cyanobacteria and bacterial heterotroph populations develop annually at the lake. These mats may exceed 5 mm in thickness and display stratification observable by eye associated with dominant bacterial phototrophic pigments. Typical mat stratification includes an orange surface layer followed by green and purple layers at increasing depth into the mat. Carbonates including aragonite and magnesite are observed within the mat and their formation is likely induced or influenced by microbial activities. While not exclusively limited to the green stratum in the mat, maximum carbonate content is within this layer. We are exploring the role Hot Lake's microbial mats play in carbon cycling within the system. Namely, we seek to understand the rates of carbon accumulation in the mat and associated sediments and the various forms this carbon takes (organic or inorganic species). We are assessing mat development, community composition, and carbon accumulation in pre-cleaned devices installed at the lake as they are colonized by native mat. We are using laser ablation isotope ratio mass spectrometry (LA-IRMS) to provide spatially-resolved stable isotope analysis of mat cross-sections. Currently, this technique permits isotope analysis at the 50 μm scale, and can provide multiple isotope analyses within the thickness of each major layer of the mat. We

  5. A Flow-through Reaction Cell that Couples Time-resolved X-ray Diffraction with Stable Isotope Analysis

    SciTech Connect

    Hanson, J.C.; Wall, A.J.; Heaney, P.J.; Mathur, R.; Post, J.E.; Eng, P.J.

    2011-04-01

    A non-metallic flow-through reaction cell is described, designed for in situ time-resolved X-ray diffraction coupled with stable isotope analysis. The experimental setup allows the correlation of Cu isotope fractionation with changes in crystal structure during copper sulfide dissolution. This flow-through cell can be applied to many classes of fluid-mineral reactions that involve dissolution or ion exchange.

  6. Validation of pentaacetylaldononitrile derivative for dual 2H gas chromatography/mass spectrometry and 13C gas chromatography/combustion/isotope ratio mass spectrometry analysis of glucose.

    PubMed

    Sauvinet, Valérie; Gabert, Laure; Qin, Du; Louche-Pélissier, Corinne; Laville, Martine; Désage, Michel

    2009-12-01

    A reference method to accurately define kinetics in response to the ingestion of glucose in terms of total, exogenous and endogenous glucose is to use stable-isotope-labelled compounds such as 2H and 13C glucose followed by gas chromatography/mass spectrometry (GC/MS) and gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS) analysis. The use of the usual pentaacetyl (5Ac) derivative generates difficulties in obtaining accurate and reproducible results due to the two chromatographic peaks for the syn and anti isomers, and to the isotopic effect occurring during acetylation. Therefore, the pentaacetylaldononitrile derivative (Aldo) was validated for both isotopes, and compared with the 5Ac derivative. A correction factor including carbon atom dilution (stoichiometric equation) and the kinetic isotopic effect (KIE) was determined. Analytical validation results for the 2H GC/MS and 13C GC/C/IRMS measurements produced acceptable results with both derivatives. When 2H enrichments of plasma samples were < or = 1 mol % excess (MPE), the repeatability (RSD(Aldo Intra assay and Intra day) <0.94%, RSD(5Ac Intra assay and Intra day) <3.29%), accuracy (Aldo <3.4%, 5Ac <29.0%), and stability of the derivatized samples were significantly better when the Aldo derivatives of the plasma samples were used (p < 0.05). When the glucose kinetics were assessed in nine human subjects, after glucose ingestion, the plasma glucose 2H enrichments were identical with both derivatives, whereas the 13C enrichments needed a correction factor to fit together. Due to KIE variation, this correction factor was not constant and had to be calculated for each batch of analyses, to obtain satisfactory results. Mean quantities of exogenous glucose exhibit marked difference (20.9 +/- 1.3g (5Ac) vs. 26.7 +/- 2.5g (Aldo)) when calculated with stoichiometric correction, but fit perfectly when calculated after application of the correc