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Sample records for accurate isotopic analysis

  1. Alternative Filament Loading Solution for Accurate Analysis of Boron Isotopes by Negative Thermal Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Dwyer, G. S.; Vengosh, A.

    2008-12-01

    The negative thermal ionization mass spectrometry technique has become the major tool for investigating boron isotopes in the environment. The high sensitivity of BO2- ionization enables measurements of ng levels of boron. However, B isotope measurement by this technique suffers from two fundamental problems (1) fractionation induced by selective ionization of B isotopes in the mass spectrometer; and (2) CNO- interference on mass 42 that is often present in some load solutions (such as B-free seawater processed through ion-exchange resin). Here we report a potentially improved methodology using an alternative filament loading solution with a recently-installed Thermo Scientific TRITON thermal ionization mass spectrometer. Our initial results suggest that this solution -- prepared by combining high-purity single- element standard solutions of Ca, Mg, Na, and K in proportions similar to those in seawater in a 5% HCl matrix -- may offer significant improvement over some other commonly used load solutions. Total loading blank is around 15pg as determined by isotope dilution (NIST952). Replicate analyses of NIST SRM951 and modern seawater thus far have yielded 11B/10B ratios of 4.0057 (±0.0008, n=14) and 4.1645 (±0.0017, n=7; δ11B=39.6 permil), respectively. Replicate analyses of samples and SRM951 yield an average standard deviation (1 σ) of approximately 0.001 (0.25 permil). Fractionation during analysis (60-90 minutes) has thus far typically been less than 0.002 (0.5 permil). The load solution delivers ionization efficiency similar to directly-loaded seawater and has negligible signal at mass 26 (CN-), a proxy for the common interfering molecular ion (CNO-) on mass 42. Standards and samples loaded with the solution behave fairly predictably during filament heating and analysis, thus allowing for the possibility of fully automated data collection.

  2. Problems in obtaining precise and accurate Sr isotope analysis from geological materials using laser ablation MC-ICPMS

    PubMed Central

    van der Wagt, B.; Koornneef, J. M.; Davies, G. R.

    2007-01-01

    This paper reviews the problems encountered in eleven studies of Sr isotope analysis using laser ablation multicollector inductively coupled plasma mass spectrometry (LA-MC-ICPMS) in the period 1995–2006. This technique has been shown to have great potential, but the accuracy and precision are limited by: (1) large instrumental mass discrimination, (2) laser-induced isotopic and elemental fractionations and (3) molecular interferences. The most important isobaric interferences are Kr and Rb, whereas Ca dimer/argides and doubly charged rare earth elements (REE) are limited to sample materials which contain substantial amounts of these elements. With modern laser (193 nm) and MC-ICPMS equipment, minerals with >500 ppm Sr content can be analysed with a precision of better than 100 ppm and a spatial resolution (spot size) of approximately 100 μm. The LA MC-ICPMS analysis of 87Sr/86Sr of both carbonate material and plagioclase is successful in all reported studies, although the higher 84Sr/86Sr ratios do suggest in some cases an influence of Ca dimer and/or argides. High Rb/Sr (>0.01) materials have been successfully analysed by carefully measuring the 85Rb/87Rb in standard material and by applying the standard-sample bracketing method for accurate Rb corrections. However, published LA-MC-ICPMS data on clinopyroxene, apatite and sphene records differences when compared with 87Sr/86Sr measured by thermal ionisation mass spectrometry (TIMS) and solution MC-ICPMS. This suggests that further studies are required to ensure that the most optimal correction methods are applied for all isobaric interferences. PMID:18080118

  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. Accurate and Precise Zinc Isotope Ratio Measurements in Urban Aerosols

    NASA Astrophysics Data System (ADS)

    Weiss, D.; Gioia, S. M. C. L.; Coles, B.; Arnold, T.; Babinski, M.

    2009-04-01

    We developed an analytical method and constrained procedural boundary conditions that enable accurate and precise Zn isotope ratio measurements in urban aerosols. We also demonstrate the potential of this new isotope system for air pollutant source tracing. The procedural blank is around 5 ng and significantly lower than published methods due to a tailored ion chromatographic separation. Accurate mass bias correction using external correction with Cu is limited to Zn sample content of approximately 50 ng due to the combined effect of blank contribution of Cu and Zn from the ion exchange procedure and the need to maintain a Cu/Zn ratio of approximately 1. Mass bias is corrected for by applying the common analyte internal standardization method approach. Comparison with other mass bias correction methods demonstrates the accuracy of the method. The average precision of δ66Zn determinations in aerosols is around 0.05 per mil per atomic mass unit. The method was tested on aerosols collected in Sao Paulo City, Brazil. The measurements reveal significant variations in δ66Zn ranging between -0.96 and -0.37 per mil in coarse and between -1.04 and 0.02 per mil in fine particular matter. This variability suggests that Zn isotopic compositions distinguish atmospheric sources. The isotopic light signature suggests traffic as the main source.

  6. 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. PMID:26751903

  7. Isotopic analysis of planetary solids

    NASA Astrophysics Data System (ADS)

    Tulej, M.; Riedo, A.; Neuland, M.; Meyer, S.; Wurz, P.

    2013-09-01

    Isotopic analysis of planetary surfaces is of considerable interest for planetology. Studies of isotope composition can deliver information on radio-isotope chronology of planetary soil/regolith, an insight to processes that altered planetary surface (space weathering) or on possible biogenic processes that occurred or still occur on the planet. Mass spectrometry is a well-suited method that delivers accurate and precise isotope composition. Among other instruments (LAZMA and LAMS), the miniature laser ablation/ionisation mass analyser, LMS developed in Bern for in situ space research can be used to measure the elemental and isotopic composition of planetary solids. LMS support mass spectrometric investigation with a mass resolution of m/Δm≈500-1500, dynamic range of at least 8 decades and detection sensitivity of ~10 ppb. Current studies of various solid materials and standard reference materials show that isotope composition can be conducted with an accuracy and precision at per mill level if the isotope concentration exceeds 10-100 ppm. Implications of the studies for in situ application are discussed.

  8. Advances in Multicollector ICPMS for precise and accurate isotope ratio measurements of Uranium isotopes

    NASA Astrophysics Data System (ADS)

    Bouman, C.; Lloyd, N. S.; Schwieters, J.

    2011-12-01

    The accurate and precise determination of uranium isotopes is challenging, because of the large dynamic range posed by the U isotope abundances and the limited available sample material. Various mass spectrometric techniques are used for the measurement of U isotopes, where TIMS is the most accepted and accurate one. Multicollector inductively coupled plasma mass spectrometry (MC-ICPMS) can offer higher productivity compared to TIMS, but is traditionally limited by low efficiency of sample utilisation. This contribution will discuss progress in MC-ICPMS for detecting 234U, 235U, 236U and 238U in various uranium reference materials from IRMM and NBL. The Thermo Scientific NEPTUNE Plus with Jet Interface offers a modified dry plasma ICP interface using a large interface pump combined with a special set of sample and skimmer cones giving ultimate sensitivity for all elements across the mass range. For uranium, an ion yield of > 3 % was reported previously [1]. The NEPTUNE Plus also offers Multi Ion Counting using discrete dynode electron multipliers as well as two high abundance-sensitivity filters to discriminate against peak tailing effects on 234U and 236U originating from the major uranium beams. These improvements in sensitivity and dynamic range allow accurate measurements of 234U, 235U and 236U abundances on very small samples and at low concentration. In our approach, minor U isotopes 234U and 236U were detected on ion counters with high abundance sensitivity filters, whereas 235U and 238U were detected on Faraday Cups using a high gain current amplifier (10e12 Ohm) for 235U. Precisions and accuracies for 234U and 236U were down to ~1%. For 235U, subpermil levels were reached.

  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. Uranium Isotopic Analysis with the FRAM Isotopic Analysis Code

    SciTech Connect

    Duc T. Vo; Thomas E. Sampson

    1999-05-01

    FRAM is the acronym for Fixed-energy Response-function Analysis with Multiple efficiency. This software was developed at Los Alamos National Laboratory originally for plutonium isotopic analysis. Later, it was adapted for uranium isotopic analysis in addition to plutonium. It is a code based on a self-calibration using several gamma-ray peaks for determining the isotopic ratios. The versatile-parameter database structure governs all facets of the data analysis. User editing of the parameter sets allows great flexibility in handling data with different isotopic distributions, interfering isotopes, and different acquisition parameters such as energy calibration and detector type.

  11. 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.

  12. 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.

  13. 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 ...

  14. 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.

  15. Selenium isotope analysis

    SciTech Connect

    Webster, C.L. Jr.; Warren, C.G.

    1981-01-01

    The isotope ratio of selenium-80 to selenium-74 was determined on an isotope ratio mass spectrometer. Samples of 2 to 4 mg of selenium were fluorinated with CoF/sub 3/ in a small disposable copper bomb. The product, SeF/sub 6/, was purified in a vacuum line by distillation. The /sup 80/Se//sup 74/Se ratio was determined on a double-collector mass spectrometer that was modified to collect either /sup 82/Se-/sup 80/Se or /sup 80/Se-/sup 74/Se ion pairs. The standard deviation of the difference between two individually fluorinated samples was about 1 per mil. Because essentially all the error was associated with the fluorination step, comparisons between a standard of SeF/sub 6/ and individually fluorinated samples can be expected to have a standard deviation of about 0.5 per mil.

  16. Analysis of accurate 13C and 18O isotope measurements of CO2 in CARIBIC aircraft air samples from the tropical troposphere, and the upper troposphere/lowermost stratosphere

    NASA Astrophysics Data System (ADS)

    Assonov, S. S.; Brenninkmeijer, C. A. M.; Schuck, T. J.; Taylor, P.

    2010-03-01

    The project CARIBIC (http://caribic-atmospheric.com) aims to study atmospheric chemistry and transport by regularly measuring many compounds in the free troposphere (FT) and the upper troposphere/lowermost stratosphere (UT/LMS) by using passenger aircraft. Here CO2 concentrations and highly accurate isotope results are presented in detail together with supporting trace gas data. 509 CARIBIC-2 samples (highest precision and accuracy δ13C(CO2) and δ18O(CO2) data) from June 2007 until March 2009, together with CARIBIC-1 samples (flights between November 1999 and April 2002, 350 samples in total, 270 for NH, mostly δ13C(CO2) data) give a fairly extensive, unique data set for the NH free troposphere and the UT/LMS region. To compare data from different years a de-trending is applied. In the UT/LMS region δ13C(CO2), δ18O(CO2) and CO2 are found to correlate well with stratospheric tracers, in particular N2O. These correlations are in good agreement with current understanding of stratospheric circulation. δ18O(CO2) appears to be a useful, hitherto unused, tracer of atmospheric transport in the UT/LMS region. By filtering out the LMS data (based on N2O distribution), the isotope variations for the free and upper troposphere are obtained. These show however little latitudinal gradient, if any, and are in good agreement with the data of selected NOAA stations in NH tropics. Correlations between δ13C(CO2) and CO2 are observed both within single flight(s) covering long distances and for certain seasons. The overall variability in de-trended δ13C(CO2) and CO2 for CARIBIC-1 and CARIBIC-2 are similar and basically agree with each other, which also underscores the high quality of measurement. Based on all correlations, we discuss that CO2 distribution in the NH FT and UT (at CARIBIC flight routes) is regulated by uplift and pole-wards transport of tropical air up to approximately 50° N. The main reasons for

  17. 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.

  18. 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

  19. 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.

  20. Procedures for accurate U and Th isotope measurements by high precision MC-ICPMS

    NASA Astrophysics Data System (ADS)

    Hoffmann, Dirk L.; Prytulak, Julie; Richards, David A.; Elliott, Tim; Coath, Christopher D.; Smart, Peter L.; Scholz, Denis

    2007-07-01

    We present multi-collector (MC) inductively coupled plasma mass spectrometry (ICPMS) protocols developed to obtain high precision, accurate determinations of U and Th isotope ratios that are applicable to a wide range of geological materials. MC-ICPMS provides a means to make high precision measurements but a recent laboratory inter-comparison, Regular European Inter-laboratory Measurement Evaluation Programme (REIMEP)-18, indicates that accurate results for U isotope ratios are not currently achieved by all facilities using MC-ICPMS. We detail a suite of protocols that can be used for a wide variety of U and Th isotope ratios and total loads. Particular attention is devoted to instrument optimisation, instrumental backgrounds, stability and memory effects, multiplier nonlinearity and yield determinations. Our results indicate that the extent of mass fractionation of U and Th analyses run under similar instrumental conditions is 0.48% per amu and 0.45% per amu, respectively, but cannot be distinguished at per mil precision levels. However, we note that multiplier-Faraday cup gain can be significantly different for U and Th by 1% and thus a U standard should not be used to correct Th measurements. For this reason, a combination of thermal ionisation mass spectrometry (TIMS) and MC-ICPMS methods have been used to determine the isotopic ratio of an in-house Th standard (TEDDi). As part of our methods, TEDDi and the U standard NBL-112a are used as bracketing standards for Th and U samples, respectively. While the in-house Th standard has 229Th-230Th-232Th composition specific for bracketing low 232Th analyses, the methods have been also successful for silicates with 230Th/232Th <10-5. Using NBL-112a, TEDDi and a gravimetrically calibrated mixed 229Th-236U spike, we demonstrate secular equilibrium in natural materials such as Table Mountain Latite and a Long Valley Glass Mountain sample with a reproducibility of ±3.8 per mil for 230Th/238U and ±2.8 per mil for 234U

  1. 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

  2. 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). PMID:27058322

  3. Molecular Isotopic Distribution Analysis (MIDAs) with adjustable mass accuracy.

    PubMed

    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. PMID:24254576

  4. 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.

  5. 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

  6. Innovations in Mass Spectrometry for Precise and Accurate Isotope Ratio Determination from Very Small Analyte Quantities (Invited)

    NASA Astrophysics Data System (ADS)

    Lloyd, N. S.; Bouman, C.; Horstwood, M. S.; Parrish, R. R.; Schwieters, J. B.

    2010-12-01

    This presentation describes progress in mass spectrometry for analysing very small analyte quantities, illustrated by example applications from nuclear forensics. In this challenging application, precise and accurate (‰) uranium isotope ratios are required from 1 - 2 µm diameter uranium oxide particles, which comprise less than 40 pg of uranium. Traditionally these are analysed using thermal ionisation mass spectrometry (TIMS), and more recently using secondary ionisation mass spectrometry (SIMS). Multicollector inductively-coupled plasma mass spectrometry (MC-ICP-MS) can offer higher productivity compared to these techniques, but is traditionally limited by low efficiency of analyte utilisation (sample through to ion detection). Samples can either be introduced as a solution, or sampled directly from solid using laser ablation. Large multi-isotope ratio datasets can help identify provenance and intended use of anthropogenic uranium and other nuclear materials [1]. The Thermo Scientific NEPTUNE Plus (Bremen, Germany) with ‘Jet Interface’ option offers unparalleled MC-ICP-MS sensitivity. An analyte utilisation of c. 4% has previously been reported for uranium [2]. This high-sensitivity configuration utilises a dry high-capacity (100 m3/h) interface pump, special skimmer and sampler cones and a desolvating nebuliser system. Coupled with new acquisition methodologies, this sensitivity enhancement makes possible the analysis of micro-particles and small sample volumes at higher precision levels than previously achieved. New, high-performance, full-size and compact discrete dynode secondary electron multipliers (SEM) exhibit excellent stability and linearity over a large dynamic range and can be configured to simultaneously measure all of the uranium isotopes. Options for high abundance-sensitivity filters on two ion beams are also available, e.g. for 236U and 234U. Additionally, amplifiers with high ohm (1012 - 1013) feedback resistors have been developed to

  7. Atom trap trace analysis of krypton isotopes

    SciTech Connect

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

    1999-11-17

    A new method of ultrasensitive isotope trace analysis has been developed. This method, based on the technique of laser manipulation of neutral atoms, has been used to count individual {sup 85}Kr and {sup 81}Kr atoms present in a natural krypton gas sample with isotopic abundances in the range of 10{sup {minus}11} and 10{sup {minus}13}, respectively. This method is free of contamination from other isotopes and elements and can be applied to several different isotope tracers for a wide range of applications. The demonstrated detection efficiency is 1 x 10{sup {minus}7}. System improvements could increase the efficiency by many orders of magnitude.

  8. 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...

  9. 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

  10. Accurate analysis of EBSD data for phase identification

    NASA Astrophysics Data System (ADS)

    Palizdar, Y.; Cochrane, R. C.; Brydson, R.; Leary, R.; Scott, A. J.

    2010-07-01

    This paper aims to investigate the reliability of software default settings in the analysis of EBSD results. To study the effect of software settings on the EBSD results, the presence of different phases in high Al steel has been investigated by EBSD. The results show the importance of appropriate automated analysis parameters for valid and reliable phase discrimination. Specifically, the importance of the minimum number of indexed bands and the maximum solution error have been investigated with values of 7-9 and 1.0-1.5° respectively, found to be needed for accurate analysis.

  11. 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.

  12. 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

  13. 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

  14. 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

  15. 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

  16. 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.

  17. 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.

  18. 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.

  19. Limitation of secondary electron multiplier non-linearity on accurate U-Th isotopic determination by MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    Shen, C.; Wu, C.; Gallet, S.; Cheng, H.; Edwards, R.; Hsieh, Y.; Lin, K.

    2008-12-01

    Contemporary multicollector-inductively coupled plasma mass spectrometry (MC-ICP-MS) with discrete dynode secondary electron multipliers (SEMs) can offer U-Th isotopic determinations with subpermil-permil- level precision in femtogram quantities. However, accurate isotopic measurement requires fully understanding SEM mass and intensity biases. In additional to dead-time effect, Richter et al (2001, Int. J. Mass Spectrom., 206, 105-127) reported a nonlinearity on SEMs produced by ETP and MasCom for count rates > 20 thousand counts per second (cps). We evaluated the possible biases for ion beams of 500- 1,600,000 cps on a latest MasCom SEM, SEV TE-Z/17, with more effective ion optical acceptance area (>50%) and better peak shape than previous models, used in a MC-ICP-MS, Thermo Fisher NEPTUNE. With the retarding potential quadruple lens (RPQ) turned off, ion beam intensity can be biased by only dead- time effect, which can be precisely corrected online or offline. With the RPQ on, two additional biases, an exponential-like increase of ion beam intensity from 100-100,000 s cps and an apparent dead-time effect (-2 to 2 ns) at high count rates, are observed. They are likely caused by the slightly defocused ions with a wide kinetic energy spread of ~5 eV, 10 times worse than that with thermal source, passing through the RPQ lens to the SEM, which is installed behind the focal plane. Fortunately, the two biases, which are stable during the daily measurements with the same settings of inlet system, source lenses, zoom optics, and RPQ, can be corrected effectively offline to earn accurate U-Th isotopic measurement.

  20. 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.

  1. 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.

  2. 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

  3. 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

  4. Accurate and precise measurement of oxygen isotopic fractions and diffusion profiles by selective attenuation of secondary ions (SASI).

    PubMed

    Téllez, Helena; Druce, John; Hong, Jong-Eun; Ishihara, Tatsumi; Kilner, John A

    2015-03-01

    The accuracy and precision of isotopic analysis in Time-of-Flight secondary ion mass spectrometry (ToF-SIMS) relies on the appropriate reduction of the dead-time and detector saturation effects, especially when analyzing species with high ion yields or present in high concentrations. Conventional approaches to avoid these problems are based on Poisson dead-time correction and/or an overall decrease of the total secondary ion intensity by reducing the target current. This ultimately leads to poor detection limits for the minor isotopes and high uncertainties of the measured isotopic ratios. An alternative strategy consists of the attenuation of those specific secondary ions that saturate the detector, providing an effective extension of the linear dynamic range. In this work, the selective attenuation of secondary ion signals (SASI) approach is applied to the study of oxygen transport properties in electroceramic materials by isotopic labeling with stable (18)O tracer and ToF-SIMS depth profiling. The better analytical performance in terms of accuracy and precision allowed a more reliable determination of the oxygen surface exchange and diffusion coefficients while maintaining good mass resolution and limits of detection for other minor secondary ion species. This improvement is especially relevant to understand the ionic transport mechanisms and properties of solid materials, such as the parallel diffusion pathways (e.g., oxygen diffusion through bulk, grain boundary, or dislocations) in electroceramic materials with relevant applications in energy storage and conversion devices. PMID:25647357

  5. Reducing the matrix effects in chemical analysis: fusion of isotope dilution and standard addition methods

    NASA Astrophysics Data System (ADS)

    Pagliano, Enea; Meija, Juris

    2016-04-01

    The combination of isotope dilution and mass spectrometry has become an ubiquitous tool of chemical analysis. Often perceived as one of the most accurate methods of chemical analysis, it is not without shortcomings. Current isotope dilution equations are not capable of fully addressing one of the key problems encountered in chemical analysis: the possible effect of sample matrix on measured isotope ratios. The method of standard addition does compensate for the effect of sample matrix by making sure that all measured solutions have identical composition. While it is impossible to attain such condition in traditional isotope dilution, we present equations which allow for matrix-matching between all measured solutions by fusion of isotope dilution and standard addition methods.

  6. 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

  7. 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

  8. 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

  9. Accurate analysis of multicomponent fuel spray evaporation in turbulent flow

    NASA Astrophysics Data System (ADS)

    Rauch, Bastian; Calabria, Raffaela; Chiariello, Fabio; Le Clercq, Patrick; Massoli, Patrizio; Rachner, Michael

    2012-04-01

    The aim of this paper is to perform an accurate analysis of the evaporation of single component and binary mixture fuels sprays in a hot weakly turbulent pipe flow by means of experimental measurement and numerical simulation. This gives a deeper insight into the relationship between fuel composition and spray evaporation. The turbulence intensity in the test section is equal to 10%, and the integral length scale is three orders of magnitude larger than the droplet size while the turbulence microscale (Kolmogorov scales) is of same order as the droplet diameter. The spray produced by means of a calibrated droplet generator was injected in a gas flow electrically preheated. N-nonane, isopropanol, and their mixtures were used in the tests. The generalized scattering imaging technique was applied to simultaneously determine size, velocity, and spatial location of the droplets carried by the turbulent flow in the quartz tube. The spray evaporation was computed using a Lagrangian particle solver coupled to a gas-phase solver. Computations of spray mean diameter and droplet size distributions at different locations along the pipe compare very favorably with the measurement results. This combined research tool enabled further investigation concerning the influencing parameters upon the evaporation process such as the turbulence, droplet internal mixing, and liquid-phase thermophysical properties.

  10. 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. PMID:25537104

  11. 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.

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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 ...

  13. 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

  14. 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.

  15. 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

  16. 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.

  17. 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%. PMID:25925860

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

    DOEpatents

    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).

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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 ...

  4. 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).

  5. 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

  6. Feasibility study of plutonium isotopic analysis of resin beads by nondestructive gamma-ray spectroscopy

    SciTech Connect

    Li, T.K.

    1985-01-01

    We have initiated a feasibility study on the use of nondestructive low-energy gamma-ray spectroscopy for plutonium isotopic analysis on resin beads. Seven resin bead samples were measured, with each sample containing an average of 9 ..mu..g of plutonium; the isotopic compositions of the samples varied over a wide range. The gamma-ray spectroscopy results, obtained from 4-h counting-time measurements, were compared with mass spectrometry results. The average ratios of gamma-ray spectroscopy to mass spectrometry were 1.014 +- 0.025 for /sup 238/Pu//sup 239/Pu, 0.996 +- 0.018 for /sup 240/Pu//sup 239/Pu, and 0.980 +- 0.038 for /sup 241/Pu//sup 239/Pu. The rapid, automated, and accurate nondestructive isotopic analysis of resin beads may be very useful to process technicians and International Atomic Energy Agency inspectors. 3 refs., 1 fig., 3 tabs.

  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. 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.

  10. Discrepancies between isotope ratio infrared spectroscopy and isotope ratio mass spectrometry for the stable isotope analysis of plant and soil waters.

    PubMed

    West, Adam G; Goldsmith, Gregory R; Brooks, Paul D; Dawson, Todd E

    2010-07-30

    The use of isotope ratio infrared spectroscopy (IRIS) for the stable hydrogen and oxygen isotope analysis of water is increasing. While IRIS has many advantages over traditional isotope ratio mass spectrometry (IRMS), it may also be prone to errors that do not impact upon IRMS analyses. Of particular concern is the potential for contaminants in the water sample to interfere with the spectroscopy, thus leading to erroneous stable isotope data. Water extracted from plant and soil samples may often contain organic contaminants. The extent to which contaminants may interfere with IRIS and thus impact upon data quality is presently unknown. We tested the performance of IRIS relative to IRMS for water extracted from 11 plant species and one organic soil horizon. IRIS deviated considerably from IRMS for over half of the samples tested, with deviations as large as 46 per thousand (delta(2)H) and 15.4 per thousand (delta(18)O) being measured. This effect was reduced somewhat by using activated charcoal to remove organics from the water; however, deviations as large as 35 per thousand (delta(2)H) and 11.8 per thousand (delta(18)O) were still measured for these cleaned samples. Interestingly, the use of activated charcoal to clean water samples had less effect than previously thought for IRMS analyses. Our data show that extreme caution is required when using IRIS to analyse water samples that may contain organic contaminants. We suggest that the development of new cleaning techniques for removing organic contaminants together with instrument-based software to flag potentially problematic samples are necessary to ensure accurate plant and soil water analyses using IRIS. PMID:20552579

  11. Accurate experimental determination of the isotope effects on the triple point temperature of water. II. Combined dependence on the 18O and 17O abundances

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

    This paper is the second of two articles on the quantification of isotope effects on the triple point temperature of water. In this second article, we address the combined effects of 18O and 17O isotopes. We manufactured five triple point cells with waters with 18O and 17O abundances exceeding widely the natural abundance range while maintaining their natural 18O/17O relationship. The 2H isotopic abundance was kept close to that of VSMOW (Vienna Standard Mean Ocean Water). These cells realized triple point temperatures ranging between  -220 μK to 1420 μK with respect to the temperature realized by a triple point cell filled with VSMOW. Our experiment allowed us to determine an accurate and reliable value for the newly defined combined 18, 17O correction parameter of AO  =  630 μK with a combined uncertainty of 10 μK. To apply this correction, only the 18O abundance of the TPW needs to be known (and the water needs to be of natural origin). Using the results of our two articles, we recommend a correction equation along with the coefficient values for isotopic compositions differing from that of VSMOW and compare the effect of this new equation on a number of triple point cells from the literature and from our own institute. Using our correction equation, the uncertainty in the isotope correction for triple point cell waters used around the world will be  <1 μK.

  12. 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.

  13. 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.

  14. The use of stable isotopes for food web analysis.

    PubMed

    Wada, E; Mizutani, H; Minagawa, M

    1991-01-01

    General aspects in isotope biogeochemistry was summarized with emphasis on delta 15N and delta 13C contents in plants and animals in natural ecosystems. In the estuary, the variation of isotope ratios were principally governed by the mixing of land-derived organic matter, marine phytoplankton, and seagrasses. A clear cut linear relationship between animal delta 15N and its trophic level was obtained in the Antarctic food chain system. Several current efforts to use the stable isotopes for food web analysis were demonstrated for some terrestrial and marine systems as well as human food web. PMID:1910519

  15. 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

  16. 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

  17. 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.

  18. 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.

  19. Water-hydrogen isotope exchange process analysis

    SciTech Connect

    Fedorchenko, O.; Alekseev, I.; Uborsky, V.

    2008-07-15

    The use of a numerical method is needed to find a solution to the equation system describing a general case of heterogeneous isotope exchange between gaseous hydrogen and liquid water in a column. A computer model of the column merely outputting the isotope compositions in the flows leaving the column, like the experimental column itself, is a 'black box' to a certain extent: the solution is not transparent and occasionally not fully comprehended. The approximate analytical solution was derived from the ZXY-diagram (McCabe-Thiele diagram), which illustrates the solution of the renewed computer model called 'EVIO-4.2' Several 'unusual' results and dependences have been analyzed and explained. (authors)

  20. Isotopic analysis of northern Himalayan gneiss domes

    NASA Astrophysics Data System (ADS)

    Hassett, W. C.

    2010-12-01

    . Statistical analysis between granitic zircon cores and host rock zircon for Leo Pargil show that 9 out of 10 REE are statistically indistinguishable, with only Pr showing significant variation in mean relative abundance. Similar results are found for analysis of host rock zircon compared between gneiss domes, where 8 out of 10 REE are statistically indistinguishable. There is little agreement between granitic zircon rims and cores, suggesting that fractionation occurred during the last magmatic event and zircon rims became enriched in HREE relative to zircon cores. These results indicate that the granitic and host rock zircon share a common source, that leucogranites within gneiss domes are most likely anatectic melts of the host rock, and that gneiss domes across the entire Himalayan orogen share a common source. U/Pb age data from zircon cores indicate that this common source can not be the Lesser Himalayan Sequence as this lithology has no ages younger than 1.5 Ga (Richards et al., 2005), but are consistent with either the GHS or the Tethyan Himalayan Sequence. Pb and Nd isotopic analyses will help to identify the source of the north Himalayan gneiss domes, and may strengthen arguments in favor of channel flow.

  1. 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.

  2. 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

  3. Molecular speciated isotope dilution mass spectrometric methods for accurate, reproducible and direct quantification of reduced, oxidized and total glutathione in biological samples.

    PubMed

    Fahrenholz, Timothy; Wolle, Mesay Mulugeta; Kingston, H M Skip; Faber, Scott; Kern, John C; Pamuku, Matt; Miller, Logan; Chatragadda, Hemasudha; Kogelnik, Andreas

    2015-01-20

    Novel protocols were developed to accurately quantify reduced (GSH), oxidized (GSSG) and total (tGSH) glutathione in biological samples using molecular speciated isotope dilution mass spectrometry (SIDMS). For GSH and GSSG measurement, the sample was spiked with isotopically enriched analogues of the analytes ((310)GSH and (616)GSSG), along with N-ethylmaleimide (NEM), and treated with acetonitrile to solubilize the endogenous analytes via protein precipitation and equilibrate them with the spikes. The supernatant was analyzed by liquid chromatography-tandem mass spectrometry (LC-MS/MS), and the analytes were quantified with simultaneous tracking and correction for auto-oxidation of GSH to GSSG. For tGSH assay, a (310)GSH-spiked sample was treated with dithiothreitol (DTT) to convert disulfide-bonded glutathione to GSH. After removing the protein, the supernatant was analyzed by LC-MS/MS and the analyte was quantified by single-spiking isotope dilution mass spectrometry (IDMS). The mathematical relationships in IDMS and SIDMS quantifications are based on isotopic ratios and do not involve calibration curves. The protocols were validated using spike recovery tests and by analyzing synthetic standard solutions. Red blood cell (RBC) and saliva samples obtained from healthy subjects, and whole blood samples collected and shipped from a remote location were analyzed. The concentrations of tGSH in the RBC and whole blood samples were 2 orders of magnitude higher than those found in saliva. The fractions of GSSG were 0.2-2.2% (RBC and blood) and 15-47% (saliva) of the free glutathione (GSH + 2xGSSG) in the corresponding samples. Up to 3% GSH was auto-oxidized to GSSG during sample workup; the highest oxidations (>1%) were in the saliva samples. PMID:25519489

  4. Development of Isotope Analysis Based on Laser Induced Fluorescence

    SciTech Connect

    Sakai, T.; Watanabe, K.; Uritani, A.; Tomita, H.; Iguchi, T.

    2009-03-17

    We have proposed Laser Induced Fluorescence analysis using Doppler Shift of laser ablated atoms for Isotope Analysis (LIF-DS-IA). This isotope analysis is expected to have a small mass discrimination effect because the detection target is fluorescence photons instead of ions, which distort the measured isotope ratio by the space charge effect. We demonstrate this technique to be feasible through the model calculations. We experimentally confirmed the fundamental behavior in LIF-DS-IA that the shift in the irradiating laser frequency corresponds to that of peak position in the time domain LIF spectra. The reason of poor mass resolution in the present system was considered to be inadequate definition in the field of view of the fluorescence detector.

  5. 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

  6. 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

  7. 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. PMID:26212984

  8. Advanced concepts for gamma ray isotopic analysis and instrumentation

    NASA Astrophysics Data System (ADS)

    Buckley, W. M.; Carlson, J. B.

    1994-07-01

    The Safeguards Technology Program at the Lawrence Livermore National Laboratory is developing actinide isotopic analysis technologies in response to needs that address issues of flexibility of analysis, robustness of analysis, ease-of-use, automation and portability. Recent developments such as the Intelligent Actinide Analysis System (IAAS), begin to address these issues. We are continuing to develop enhancements on this and other instruments that improve ease-of-use, automation and portability. Requests to analyze samples with unusual isotopics, contamination, or containers have made us aware of the need for more flexible and robust analysis. We have modified the MGA program to extend its plutonium isotopic analysis capability to samples with greater Am-241 content or U isotopics. We are looking at methods for dealing with tantalum or lead contamination and contamination with high-energy gamma emitters, such as U-233. We are looking at ways to allow the program to use additional information about the sample to further extend the domain of analyzable samples. These unusual analyses will come from the domain of samples that need to be measured because of complex reconfiguration or environmental cleanup.

  9. 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

  10. 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.

  11. 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

  12. 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.

  13. 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)

  14. Kinetic isotope effect of the (16)O + (36)O2 and (18)O + (32)O2 isotope exchange reactions: Dominant role of reactive resonances revealed by an accurate time-dependent quantum wavepacket study.

    PubMed

    Sun, Zhigang; Yu, Dequan; Xie, Wenbo; Hou, Jiayi; Dawes, Richard; Guo, Hua

    2015-05-01

    The O + O2 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 (18)O + (32)O2 and (16)O + (36)O2 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. PMID:25956105

  15. Kinetic isotope effect of the 16O + 36O2 and 18O + 32O2 isotope exchange reactions: Dominant role of reactive resonances revealed by an accurate time-dependent quantum wavepacket study

    NASA Astrophysics Data System (ADS)

    Sun, Zhigang; Yu, Dequan; Xie, Wenbo; Hou, Jiayi; Dawes, Richard; Guo, Hua

    2015-05-01

    The O + O2 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 18O + 32O2 and 16O + 36O2 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.

  16. 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. PMID:26033549

  17. Krypton isotope analysis using near-resonant stimulated Raman spectroscopy

    SciTech Connect

    Whitehead, C.A.; Cannon, B.D.; Wacker, J.F.

    1994-12-01

    A method for measuring low relative abundances of {sup 85}Kr in one liter or less samples of air has been under development here at Pacific Northwest Laboratory. The goal of the Krypton Isotope Laser Analysis (KILA) method is to measure ratios of 10{sup {minus}10} or less of {sup 85}Kr to more abundant stable krypton. Mass spectrometry and beta counting are the main competing technologies used in rare-gas trace analysis and are limited in application by such factors as sample size, counting times, and selectivity. The use of high-resolution lasers to probe hyperfine levels to determine isotopic abundance has received much attention recently. In this study, we report our progress on identifying and implementing techniques for trace {sup 85}Kr analysis on small gas samples in a static cell as well as limitations on sensitivity and selectivity for the technique. High-resolution pulsed and cw lasers are employed in a laser-induced fluorescence technique that preserves the original sample. This technique, is based on resonant isotopic depletion spectroscopy (RIDS) in which one isotope is optically depleted while preserving the population of a less abundant isotope. The KILA method consists of three steps. In the first step, the 1s{sub 5} metastable level of krypton is populated via radiative cascade following two-photon excitation of the 2p{sub 6} energy level. Next, using RBDS, the stable krypton isotopes are optically depleted to the ground state through the 1s{sub 4} level with the bulk of the {sup 85}Kr population being preserved. Finally, the remaining metastable population is probed to determine {sup 85}Kr concentration. The experimental requirements for each of these steps are outlined below.

  18. 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...

  19. 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

  20. 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

  1. 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.

  2. In Situ Oxygen Isotope Analysis of Conodonts by SIMS and Its Implication for Paleo-sea Surface Temperature

    NASA Astrophysics Data System (ADS)

    Zhao, L.; Chen, J.; Chen, Z.; Chen, Y.; Wang, R.; Tang, G.; Li, X.; Lv, J.; Zhuang, X.

    2013-12-01

    Oxygen isotope composition of biogenic apatite is potentially useful in paleotemperature reconstruction of contemporaneous surface seawater temperature (SST). Combined with abundant researches on their biostratigraphy, the geochemical analysis of conodonts contains more significant signatures indicating paleoenvironmental changes. However, the small size is always a limited factor for the accurate analysis. In this work, we tested the oxygen isotope of conodont using Cameca IMS-1280 secondary ion mass spectrometry (SIMS) for the first time and acquired reliable records on contemporaneous SST. We found that SST raised rapidly following the Late Permian biocrisis, implying that the rapid increase in paleo-temperature may have been one of the crucial killers responsible for the Permian-Triassic mass extinction. Compared with the previous Ag3PO4 method, our analysis technique is faster with both high resolution and high spatial resolution, so we can avoid the position easily contaminated during the late diagensis and acquire the original oxygen isotopic compositions.

  3. Inductively coupled plasma mass spectrometry applied to isotopic analysis of iron in human fecal matter

    SciTech Connect

    Ting, B.T.G.; Janghorbani, M.

    1986-06-01

    Inductively coupled plasma mass spectrometry combined with stable isotope dilution is applied to accurate isotopic analysis of human fecal matter for /sup 54/Fe and /sup 58/Fe. Argon plasma generated interferences are of minor concern. The interference from /sup 54/Cr can be corrected instrumentally, whereas /sup 58/Ni must be removed chemically. The ratio of the stable isotopes of interest can be measured routinely with a relative standard deviation of about 1%. The overall accuracy of the method for quantitative isotopic analyses is evaluated in Standard Reference Material (SRM) 1577a (Bovine Liver), fecal homogenate subsamples, and synthetic solutions of iron. For SRM 1577a, the respective comparisons are (..mu..g/g) 192.2 +/- 2.2 (present method) vs. 194 +/- 20 (certified value). For the fecal matrix, the present method yields (..mu..g/mL) 15.14 +/- 0.36 vs. 15.82 +/- 0.48 based on atomic absorption spectrophotometry. For an iron solution (250 ppm), replicate analyses yield the value of 245.4 +/- 1.5 ppm.

  4. Internal Referencing for ¹³C Position-Specific Isotope Analysis Measured by NMR Spectrometry.

    PubMed

    Bayle, Kevin; Grand, Mathilde; Chaintreau, Alain; Robins, Richard J; Fieber, Wolfgang; Sommer, Horst; Akoka, Serge; Remaud, Gérald S

    2015-08-01

    The intramolecular (13)C composition of a molecule retains evidence relevant to its (bio)synthetic history and can provide valuable information in numerous fields ranging from biochemistry to environmental sciences. Isotope ratio monitoring by (13)C NMR spectrometry (irm-(13)C NMR) is a generic method that offers the potential to conduct (13)C position-specific isotope analysis with a precision better than 1‰. Until now, determining absolute values also required measurement of the global (or bulk) (13)C composition (δ(13)Cg) by mass spectrometry. In a radical new approach, it is shown that an internal isotopic chemical reference for irm-(13)C NMR can be used instead. The strategy uses (1)H NMR to quantify both the number of moles of the reference and of the studied compound present in the NMR tube. Thus, the sample preparation protocol is greatly simplified, bypassing the previous requirement for precise purity and mass determination. The key to accurate results is suppressing the effect of radiation damping in (1)H NMR which produces signal distortion and alters quantification. The methodology, applied to vanillin with dimethylsulfone as an internal standard, has an equivalent accuracy (<1‰) to that of the conventional approach. Hence, it was possible to clearly identify vanillin from different origins based on the (13)C isotopic profiles. PMID:26158226

  5. 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

  6. 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.

  7. 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

  8. 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

  9. 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

  10. 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. PMID:25621380

  11. 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

  12. 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

  13. 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.

  14. 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.

  15. 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.

  16. 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.``

  17. 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.

  18. 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

  19. Accurate Analysis and Computer Aided Design of Microstrip Dual Mode Resonators and Filters.

    NASA Astrophysics Data System (ADS)

    Grounds, Preston Whitfield, III

    1995-01-01

    Microstrip structures are of interest due to their many applications in microwave circuit design. Their small size and ease of connection to both passive and active components make them well suited for use in systems where size and space is at a premium. These include satellite communication systems, radar systems, satellite navigation systems, cellular phones and many others. In general, space is always a premium for any mobile system. Microstrip resonators find particular application in oscillators and filters. In typical filters each microstrip patch corresponds to one resonator. However, when dual mode patches are employed, each patch acts as two resonators and therefore reduces the amount of space required to build the filter. This dissertation focuses on the accurate electromagnetic analysis of the components of planar dual mode filters. Highly accurate analyses are required so that the resonator to resonator coupling and the resonator to input/output can be predicted with precision. Hence, filters can be built with a minimum of design iterations and tuning. The analysis used herein is an integral equation formulation in the spectral domain. The analysis is done in the spectral domain since the Green's function can be derived in closed form, and the spatial domain convolution becomes a simple product. The resulting set of equations is solved using the Method of Moments with Galerkin's procedure. The electromagnetic analysis is applied to range of problems including unloaded dual mode patches, dual mode patches coupled to microstrip feedlines, and complete filter structures. At each step calculated results are compared to measured results and good agreement is found. The calculated results are also compared to results from the circuit analysis program HP EESOF^{ rm TM} and again good agreement is found. A dual mode elliptic filter is built and good performance is obtained.

  20. 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.

  1. Accurate variational calculations and analysis of the HOCl vibrational energy spectrum

    SciTech Connect

    Skokov, S.; Qi, J.; Bowman, J.M.; Yang, C.; Gray, S.K.; Peterson, K.A. |; Mandelshtam, V.A.

    1998-12-01

    Large scale variational calculations for the vibrational states of HOCl are performed using a recently developed, accurate {ital ab initio} potential energy surface. Three different approaches for obtaining vibrational states are employed and contrasted; a truncation/recoupling scheme with direct diagonalization, the Lanczos method, and Chebyshev iteration with filter diagonalization. The complete spectrum of bound states for nonrotating HOCl is computed and analyzed within a random matrix theory framework. This analysis indicates almost entirely regular dynamics with only a small degree of chaos. The nearly regular spectral structure allows us to make assignments for the most significant part of the spectrum, based on analysis of coordinate expectation values and eigenfunctions. Ground state dipole moments and dipole transition probabilities are also calculated using accurate {ital ab initio} data. Computed values are in good agreement with available experimental data. Some exact rovibrational calculations for J=1, including Coriolis coupling, are performed. The exact results are nearly identical with those obtained from the adiabatic rotation approximation and very close to those from the centrifugal sudden approximation, thus indicating a very small degree of asymmetry and Coriolis coupling for the HOCl molecule. {copyright} {ital 1998 American Institute of Physics.}

  2. 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.

  3. Carbon isotope ratio analysis of steroids by high-temperature liquid chromatography-isotope ratio mass spectrometry.

    PubMed

    Zhang, Lijun; Thevis, Mario; Piper, Thomas; Jochmann, Maik A; Wolbert, J Benjamin; Kujawinski, Dorothea M; Wiese, Steffen; Teutenberg, Thorsten; Schmidt, Torsten C

    2014-03-01

    Generally, compound-specific isotope analysis of steroids is carried out by gas chromatography combined with isotope ratio mass spectrometry. Thus, a derivatization of the steroids prior to the measurement is compulsory, and a correction of the isotopic data is often necessary. To overcome this limitation, we present a new approach of high-temperature liquid chromatography coupled with photodiode array detection and isotope ratio mass spectrometry (HT-LC/PDA/IRMS) for the carbon isotope ratio analysis of unconjugated steroids. A steroid mixture containing 19-norandrosterone, testosterone, epitestosterone, androsterone, and 5β-pregnane-3α,17α,20α-triol was fully separated on a C4 column under high-temperature elution with water as the sole eluent. The accuracy for isotope analysis (±0.5 ‰) was around 20 μg g(-1) for testosterone, epitestosterone (79 ng steroid absolute on column), and 30 μg g(-1) for 19-norandrosterone, androsterone, and 5β-pregnane-3α,17α,20α-triol (119 ng steroid absolute on column). The applicability of the method was tested by measuring a pharmaceutical gel containing testosterone. With this work, the scope of LC/IRMS applications has been extended to nonpolar compounds. PMID:24491121

  4. Stable isotope labeling - Liquid chromatography/mass spectrometry for quantitative analysis of androgenic and progestagenic steroids.

    PubMed

    Guo, Ning; Liu, Ping; Ding, Jun; Zheng, Shu-Jian; Yuan, Bi-Feng; Feng, Yu-Qi

    2016-01-28

    Steroid hormones play important roles in mammal at very low concentrations and are associated with numerous endocrinology and oncology diseases. Therefore, quantitative analysis of steroid hormones can provide crucial information for uncovering underlying mechanisms of steroid hormones related diseases. In the current study, we developed a sensitive method for the detection of steroid hormones (progesterone, dehydroepiandrosterone, testosterone, pregnenolone, 17-hydroxyprogesterone, androstenedione and 17α-hydroxypregnenolone) in body fluids by stable isotope labeling coupled with liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS) analysis. In this respect, a pair of isotopes labeling reagents, Girard reagent P (GP) and d5-Girard reagent P (d5-GP), were synthesized and utilized to label steroid hormones in follicular fluid samples and steroid hormone standards, respectively. The heavy labeled standards were used as internal standards for quantification to minimize quantitation deviation in MS analysis due to the matrix and ion suppression effects. The ionization efficiencies of steroid hormones were greatly improved by 4-504 folds through the introduction of a permanent charged moiety of quaternary ammonium from GP. Using the developed method, we successfully quantified steroid hormones in human follicular fluid. We found that the contents of testosterone and androstenedione exhibited significant increase while the content of pregnenolone had significant decrease in follicular fluid of polycystic ovarian syndrome (PCOS) patients compared with healthy controls, indicating that these steroid hormones with significant change may contribute to the pathogenesis of PCOS. Taken together, the developed stable isotope labeling coupled LC-ESI-MS/MS analysis demonstrated to be a promising method for the sensitive and accurate determination of steroid hormones, which may facilitate the in-depth investigation of steroid hormones related

  5. Gamma-ray isotopic analysis development at Los Alamos

    SciTech Connect

    Thomas E. Sampson

    1999-11-01

    This report describes the development history and characteristics of software developed in the Safeguards Science and Technology group at Los Alamos for gamma-ray isotopic analysis. This software analyzes the gamma-ray spectrum from measurements performed on actinide samples (principally plutonium and uranium) of arbitrary size, geometry, and physical and chemical composition. The results are obtained without calibration using only fundamental tabulated nuclear constants. Characteristics of the current software versions are discussed in some detail and many examples of implemented measurement systems are shown.

  6. Trace determination of zinc by substoichiometric isotope dilution analysis

    SciTech Connect

    Sandhya, D.; Priya, S.; Subramanian, M.O.S.

    1996-09-01

    A radiometric method based on substoichiometric isotope dilution analysis using 1,10-phenanthroline and a substoichiometric amount of eosin was developed for determining trace amounts of zinc. Evaluation of various metal ion interferences shows that as little as 0.2 {mu}g Zn could be determined in an aqueous-phase volume of 60 mL. The method has been successfully applied to the determination of Zn in city waste incineration ash, cadmium metal, Fourts-B tablets, Boro-plus ointment, and magnesium alloy samples. 12 refs., 3 figs., 3 tabs.

  7. 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

  8. 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.

  9. Accurate rotor loads prediction using the FLAP (Force and Loads Analysis Program) dynamics code

    SciTech Connect

    Wright, A.D.; Thresher, R.W.

    1987-10-01

    Accurately predicting wind turbine blade loads and response is very important in predicting the fatigue life of wind turbines. There is a clear need in the wind turbine community for validated and user-friendly structural dynamics codes for predicting blade loads and response. At the Solar Energy Research Institute (SERI), a Force and Loads Analysis Program (FLAP) has been refined and validated and is ready for general use. Currently, FLAP is operational on an IBM-PC compatible computer and can be used to analyze both rigid- and teetering-hub configurations. The results of this paper show that FLAP can be used to accurately predict the deterministic loads for rigid-hub rotors. This paper compares analytical predictions to field test measurements for a three-bladed, upwind turbine with a rigid-hub configuration. The deterministic loads predicted by FLAP are compared with 10-min azimuth averages of blade root flapwise bending moments for different wind speeds. 6 refs., 12 figs., 3 tabs.

  10. 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.

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

    PubMed

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

    2016-06-21

    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. PMID:27227661

  12. Simultaneous sample preparation and species-specific isotope dilution mass spectrometry analysis of monomethylmercury and tributyltin in a certified oyster tissue.

    PubMed

    Monperrus, M; Rodriguez Martin-Doimeadios, R C; Scancar, J; Amouroux, D; Donard, O F X

    2003-08-15

    A rapid, accurate, sensitive, and simple method for simultaneous speciation analysis of mercury and tin in biological samples has been developed. Integrated simultaneous sample preparation for tin and mercury species includes open focused microwave extraction and derivatization via ethylation. Capillary gas chromatography-inductively plasma mass spectrometry (CGC-ICPMS) conditions and parameters affecting the analytical performance were carefully optimized both for species-specific isotope dilution analysis of MMHg and TBT and for conventional analysis of MBT and DBT201Hg-enriched monomethylmercury and 117Sn-enriched tributyltin were used for species-specific isotope dilution mass spectrometry (SIDMS) analysis. As important, accurate isotope dilution analysis requires equilibration between the spike and the analyte to achieve successful analytical procedures. Since the spike stabilization and solubilization are the most critical and time-consuming steps in isotope dilution analysis, different spiking procedures were tested. Simultaneous microwave-assisted spike stabilization and solubilization can be achieved within less than 5 min. This study originally introduces a method for the simultaneous speciation and isotope dilution of mercury and tin in biological tissues. The sample throughput of the procedure was drastically reduced by fastening sample preparation and GC separation steps. The accuracy of the method was tested by both external calibration analysis and species-specific isotope dilution analysis using the first biological reference material certified for multielemental speciation (oyster tissue, CRM 710, IRMM). The results obtained demonstrate that isotope dilution analysis is a powerful method allowing the simultaneous speciation of TBT and MMHg with high precision and excellent accuracy. Analytical problems related to low recovery during sample preparation are thus minimized by SIDMS. In addition, a rapid procedure allows us to establish a performant

  13. 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.

  14. Novel methods for accurate identification, isolation, and genomic analysis of symptomatic microenvironments in atherosclerotic arteries.

    PubMed

    Slevin, Mark; Baldellou, Maribel; Hill, Elspeth; Alexander, Yvonne; McDowell, Garry; Murgatroyd, Christopher; Carroll, Michael; Degens, Hans; Krupinski, Jerzy; Rovira, Norma; Chowdhury, Mohammad; Serracino-Inglott, Ferdinand; Badimon, Lina

    2014-01-01

    A challenge facing surgeons is identification and selection of patients for carotid endarterectomy or coronary artery bypass/surgical intervention. While some patients with atherosclerosis develop unstable plaques liable to undergo thrombosis, others form more stable plaques and are asymptomatic. Identification of the cellular signaling mechanisms associated with production of the inflammatory, hemorrhagic lesions of mature heterogenic plaques will help significantly in our understanding of the differences in microenvironment associated with development of regions susceptible to rupture and thrombosis and may help to predict the risk of plaque rupture and guide surgical intervention to patients who will most benefit. Here, we demonstrate detailed and novel methodologies for successful and, more importantly, accurate and reproducible extraction, sampling, and analysis of micro-regions in stable and unstable coronary/carotid arteries. This information can be applied to samples from other origins and so should be useful for scientists working with micro-isolation techniques in all fields of biomedical science. PMID:24510873

  15. 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

  16. 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

  17. 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

  18. Analysis and accurate quantification of CpG methylation by MALDI mass spectrometry

    PubMed Central

    Tost, Jörg; Schatz, Philipp; Schuster, Matthias; Berlin, Kurt; Gut, Ivo Glynne

    2003-01-01

    As the DNA sequence of the human genome is now nearly finished, the main task of genome research is to elucidate gene function and regulation. DNA methylation is of particular importance for gene regulation and is strongly implicated in the development of cancer. Even minor changes in the degree of methylation can have severe consequences. An accurate quantification of the methylation status at any given position of the genome is a powerful diagnostic indicator. Here we present the first assay for the analysis and precise quantification of methylation on CpG positions in simplex and multiplex reactions based on matrix-assisted laser desorption/ ionisation mass spectrometry detection. Calibration curves for CpGs in two genes were established and an algorithm was developed to account for systematic fluctuations. Regression analysis gave R2 ≥ 0.99 and standard deviation around 2% for the different positions. The limit of detection was ∼5% for the minor isomer. Calibrations showed no significant differences when carried out as simplex or multiplex analyses. All variable parameters were thoroughly investigated, several paraffin-embedded tissue biopsies were analysed and results were verified by established methods like analysis of cloned material. Mass spectrometric results were also compared to chip hybridisation. PMID:12711695

  19. 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

  20. Accurate optical analysis of single-molecule entrapment in nanoscale vesicles.

    PubMed

    Reiner, Joseph E; Jahn, Andreas; Stavis, Samuel M; Culbertson, Michael J; Vreeland, Wyatt N; Burden, Daniel L; Geist, Jon; Gaitan, Michael

    2010-01-01

    We present a nondestructive method to accurately characterize low analyte concentrations (0-10 molecules) in nanometer-scale lipid vesicles. Our approach is based on the application of fluorescence fluctuation analysis (FFA) and multiangle laser light scattering (MALLS) in conjunction with asymmetric field flow fractionation (AFFF) to measure the entrapment efficiency (the ratio of the concentration of encapsulated dye to the initial bulk concentration) of an ensemble of liposomes with an average diameter less than 100 nm. Water-soluble sulforhodamine B (SRB) was loaded into the aqueous interior of nanoscale liposomes synthesized in a microfluidic device. A confocal microscope was used to detect a laser-induced fluorescence signal resulting from both encapsulated and unencapsulated SRB molecules. The first two cumulants of this signal along with the autocorrelation function (ACF) were used to quantify liposome entrapment efficiency. Our analysis moves beyond typical, nonphysical assumptions of equal liposome size and brightness. These advances are essential for characterizing liposomes in the single-molecule encapsulation regime. Our work has further analytical impact because it could increase the interrogation time of free-solution molecular analysis by an order of magnitude and form the basis for the development of liposome standard reference materials. PMID:19950933

  1. Can CO2 assimilation in maize leaves be predicted accurately from chlorophyll fluorescence analysis?

    PubMed

    Edwards, G E; Baker, N R

    1993-08-01

    Analysis is made of the energetics of CO2 fixation, the photochemical quantum requirement per CO2 fixed, and sinks for utilising reductive power in the C4 plant maize. CO2 assimilation is the primary sink for energy derived from photochemistry, whereas photorespiration and nitrogen assimilation are relatively small sinks, particularly in developed leaves. Measurement of O2 exchange by mass spectrometry and CO2 exchange by infrared gas analysis under varying levels of CO2 indicate that there is a very close relationship between the true rate of O2 evolution from PS II and the net rate of CO2 fixation. Consideration is given to measurements of the quantum yields of PS II (φ PS II) from fluorescence analysis and of CO2 assimilation ([Formula: see text]) in maize over a wide range of conditions. The[Formula: see text] ratio was found to remain reasonably constant (ca. 12) over a range of physiological conditions in developed leaves, with varying temperature, CO2 concentrations, light intensities (from 5% to 100% of full sunlight), and following photoinhibition under high light and low temperature. A simple model for predicting CO2 assimilation from fluorescence parameters is presented and evaluated. It is concluded that under a wide range of conditions fluorescence parameters can be used to predict accurately and rapidly CO2 assimilation rates in maize. PMID:24317706

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

    PubMed

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

    2015-05-01

    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 oxidised 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 <50mg/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 labelled standards for quantitative characterisation of processing-induced volatile generation across related foodstuffs, and verify the origin of specific volatiles from parent n-3 fatty acids. PMID:25529686

  3. 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

  4. Secondary ionization mass spectrometric analysis of impurity element isotope ratios in nuclear reactor materials

    NASA Astrophysics Data System (ADS)

    Gerlach, D. C.; Cliff, J. B.; Hurley, D. E.; Reid, B. D.; Little, W. W.; Meriwether, G. H.; Wickham, A. J.; Simmons, T. A.

    2006-07-01

    During reactor operations and fuel burn up, some isotopic abundances change due to nuclear reactions and provide sensitive indicators of neutron fluence and fuel burnup. Secondary ion mass spectrometry (SIMS) analysis has been used to measure isotope ratios of selected impurity elements in irradiated nuclear reactor graphite. Direct SIMS measurements were made in graphite samples, following shaping and surface cleaning. Models predicting local fuel burnup based on isotopic measurements of B and Li isotopes by SIMS agreed well with U and Pu isotopic measurements obtained by thermal ionization mass spectrometry (TIMS).

  5. A virtual environment for the accurate geologic analysis of Martian terrain

    NASA Astrophysics Data System (ADS)

    Traxler, Christoph; Paar, Gerhard; Gupta, Sanjeev; Hesina, Gerd; Sander, Kathrin; Barnes, Rob; Nauschnegg, Bernhard; Muller, Jan-Peter; Tao, Yu

    2015-04-01

    Remote geology on planetary surfaces requires immersive presentation of the environment to be investigated. Three-dimensional (3D) processing of images from rovers and satellites enables to reconstruct terrain in virtual space on Earth for scientific analysis. In this paper we present a virtual environment that allows to interactively explore 3D-reconstructed Martian terrain and perform accurate measurements on the surface. Geologists do not only require line-of-sight measurements between two points but much more the projected line-of-sight on the surface between two such points. Furthermore the tool supports to define paths of several points. It is also important for geologists to annotate the terrain they explore, especially when collaborating with colleagues. The path tool can also be used to separate geological layers or surround areas of interest. They can be linked with a text label directly positioned in 3D space and always oriented towards the viewing direction. All measurements and annotations can be maintained by a graphical user interface and used as landmarks, i.e. it is possible to fly to the corresponding locations. The virtual environment is fed with 3D vision products from rover cameras, placed in the 3D context gained from satellite images (digital elevations models and corresponding ortho images). This allows investigations in various scales from planet to microscopic level in a seamless manner. The modes of exploitation and added value of such an interactive means are manifold. The visualisation products enable us to map geological surfaces and rock layers over large areas in a quantitative framework. Accurate geometrical relationships of rock bodies especially for sedimentary layers can be reconstructed and the relationships between superposed layers can be established. Within sedimentary layers, we can delineate sedimentary faces and other characteristics. In particular, inclination of beds which may help ascertain flow directions can be

  6. 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

  7. Accurate Quantification of High Density Lipoprotein Particle Concentration by Calibrated Ion Mobility Analysis

    PubMed Central

    Hutchins, Patrick M.; Ronsein, Graziella E.; Monette, Jeffrey S.; Pamir, Nathalie; Wimberger, Jake; He, Yi; Anantharamaiah, G.M.; Kim, Daniel Seung; Ranchalis, Jane E.; Jarvik, Gail P.; Vaisar, Tomas; Heinecke, Jay W.

    2015-01-01

    Background It is critical to develop new metrics to determine whether high density lipoprotein (HDL) is cardioprotective in humans. One promising approach is HDL particle concentration (HDL-P) – the size and concentration of HDL in plasma or serum. However, the two methods currently used to determine HDL-P yield concentrations that differ more than 5-fold. We therefore developed and validated an improved approach to quantify HDL-P, termed calibrated ion mobility analysis (calibrated IMA). Methods HDL was isolated from plasma by ultracentrifugation, introduced into the gas phase with electrospray ionization, separated by size, and quantified by particle counting. A calibration curve constructed with purified proteins was used to correct for the ionization efficiency of HDL particles. Results The concentrations of gold nanoparticles and reconstituted HDLs measured by calibrated IMA were indistinguishable from concentrations determined by orthogonal methods. In plasma of control (n=40) and cerebrovascular disease (n=40) subjects, three subspecies of HDL were reproducibility measured, with an estimated total HDL-P of 13.4±2.4 µM (mean±SD). HDL-C accounted for 48% of the variance in HDL-P. HDL-P was significantly lower in subjects with cerebrovascular disease, and this difference remained significant after adjustment for HDL cholesterol levels. Conclusions Calibrated IMA accurately and reproducibly determined the concentration of gold nanoparticles and synthetic HDL, strongly suggesting the method could accurately quantify HDL particle concentration. Importantly, the estimated stoichiometry of apoA-I determined by calibrated IMA was 3–4 per HDL particle, in excellent agreement with current structural models. Furthermore, HDL-P associated with cardiovascular disease status in a clinical population independently of HDL cholesterol. PMID:25225166

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

    PubMed

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

    2016-07-13

    Quantitative analysis of specifically deuterated compounds can be achieved by a number of conventional methods, such as mass spectroscopy, or by quantifying the residual (1)H NMR signals compared to signals from internal standards. However, site specific quantification using these methods becomes challenging when dealing with non-specifically or randomly deuterated compounds that are produced by metal catalyzed hydrothermal reactions in D2O, one of the most convenient deuteration methods. In this study, deuterium-induced NMR isotope shifts of quaternary (13)C resonances neighboring deuterated sites have been utilized to quantify the degree of isotope labeling of molecular sites in non-specifically deuterated molecules. By probing (13)C NMR signals while decoupling both proton and deuterium nuclei, it is possible to resolve (13)C resonances of the different isotopologues based on the isotopic shifts and the degree of deuteration of the carbon atoms. We demonstrate that in different isotopologues, the same quaternary carbon, neighboring partially deuterated carbon atoms, are affected to an equal extent by relaxation. Decoupling both nuclei ((1)H, (2)H) resolves closely separated quaternary (13)C signals of the different isotopologues, and allows their accurate integration and quantification under short relaxation delays (D1 = 1 s) and hence fast accumulative spectral acquisition. We have performed a number of approaches to quantify the deuterium content at different specific sites to demonstrate a convenient and generic analysis method for use in randomly deuterated molecules, or in cases of specifically deuterated molecules where back-exchange processes may take place during work up. PMID:27237841

  9. 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

  10. 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.

  11. Phase-function normalization for accurate analysis of ultrafast collimated radiative transfer.

    PubMed

    Hunter, Brian; Guo, Zhixiong

    2012-04-20

    The scattering of radiation from collimated irradiation is accurately treated via normalization of phase function. This approach is applicable to any numerical method with directional discretization. In this study it is applied to the transient discrete-ordinates method for ultrafast collimated radiative transfer analysis in turbid media. A technique recently developed by the authors, which conserves a phase-function asymmetry factor as well as scattered energy for the Henyey-Greenstein phase function in steady-state diffuse radiative transfer analysis, is applied to the general Legendre scattering phase function in ultrafast collimated radiative transfer. Heat flux profiles in a model tissue cylinder are generated for various phase functions and compared to those generated when normalization of the collimated phase function is neglected. Energy deposition in the medium is also investigated. Lack of conservation of scattered energy and the asymmetry factor for the collimated scattering phase function causes overpredictions in both heat flux and energy deposition for highly anisotropic scattering media. In addition, a discussion is presented to clarify the time-dependent formulation of divergence of radiative heat flux. PMID:22534933

  12. 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

  13. 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.

  14. 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.

  15. Multi-element compound specific stable isotope analysis of volatile organic compounds at trace levels in groundwater samples

    NASA Astrophysics Data System (ADS)

    Herrero-Martín, Sara; Nijenhuis, Ivonne; Schmidt, Marie; Wolfram, Diana; Richnow, Hans. H.; Gehre, Matthias

    2013-04-01

    Groundwater pollution remains one of the major environmental and health concerns. A thorough understanding of sources, sinks and transformation processes of groundwater contaminants is needed to improve risk management evaluation, and to design efficient remediation and water treatment strategies. Isotopic tools provide unique information for an in-depth understanding of the fate of organic chemicals in the environment. During the last decades compound specific isotope analysis (CSIA) of complex mixtures, using gas chromatography-isotope ratio mass spectrometry (GC-IRMS), has gained popularity for the characterization and risk assessment of hazardous waste sites and for isotope forensics of organic contaminants. Multi-element isotope fingerprinting of organic substances provides a more robust framework for interpretation than the isotope analysis of only one element. One major challenge for application of CSIA is the analysis of trace levels of organic compounds in environmental matrices. It is necessary to inject 1 nmol carbon or 8 nmol hydrogen on column, to obtain an accurate and precise measurement of the isotope ratios, which is between two and three orders of magnitude larger than the amount of compound needed for conventional analysis of compound concentrations. Therefore, efficient extraction and pre-concentration techniques have to be integrated with GC-IRMS. Further research is urgently needed in this field, to evaluate the potential of novel and environmental-friendly sample pre-treatment techniques for CSIA to lower the detection limits and extending environmental applications. In this study, the novel coupling of a headspace autosampler (HS) with a programmed temperature vaporizer (PTV), allowing large volume injection of headspace samples, is proposed to improve the sensitivity of CSIA. This automatic, fast and solvent free strategy provides a significant increase on the sensitivity of GC-based methods maintaining the simple headspace instrumentation

  16. 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.

  17. 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. PMID:25967147

  18. Mapping photoautotrophic metabolism with isotopically nonstationary (13)C flux analysis.

    PubMed

    Young, Jamey D; Shastri, Avantika A; Stephanopoulos, Gregory; Morgan, John A

    2011-11-01

    Understanding in vivo regulation of photoautotrophic metabolism is important for identifying strategies to improve photosynthetic efficiency or re-route carbon fluxes to desirable end products. We have developed an approach to reconstruct comprehensive flux maps of photoautotrophic metabolism by computational analysis of dynamic isotope labeling measurements and have applied it to determine metabolic pathway fluxes in the cyanobacterium Synechocystis sp. PCC6803. Comparison to a theoretically predicted flux map revealed inefficiencies in photosynthesis due to oxidative pentose phosphate pathway and malic enzyme activity, despite negligible photorespiration. This approach has potential to fill important gaps in our understanding of how carbon and energy flows are systemically regulated in cyanobacteria, plants, and algae. PMID:21907300

  19. 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.

  20. 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.

  1. Phosphorylation-Specific MS/MS Scoring for Rapid and Accurate Phosphoproteome Analysis

    PubMed Central

    Payne, Samuel H.; Yau, Margaret; Smolka, Marcus B.; Tanner, Stephen; Zhou, Huilin; Bafna, Vineet

    2008-01-01

    The promise of mass spectrometry as a tool for probing signal-transduction is predicated on reliable identification of post-translational modifications. Phosphorylations are key mediators of cellular signaling, yet are hard to detect, partly because of unusual fragmentation patterns of phosphopeptides. In addition to being accurate, MS/MS identification software must be robust and efficient to deal with increasingly large spectral data sets. Here, we present a new scoring function for the Inspect software for phosphorylated peptide tandem mass spectra for ion-trap instruments, without the need for manual validation. The scoring function was modeled by learning fragmentation patterns from 7677 validated phosphopeptide spectra. We compare our algorithm against SEQUEST and X!Tandem on testing and training data sets. At a 1% false positive rate, Inspect identified the greatest total number of phosphorylated spectra, 13% more than SEQUEST and 39% more than X!Tandem. Spectra identified by Inspect tended to score better in several spectral quality measures. Furthermore, Inspect runs much faster than either SEQUEST or X!Tandem, making desktop phosphoproteomics feasible. Finally, we used our new models to reanalyze a corpus of 423 000 LTQ spectra acquired for a phosphoproteome analysis of Saccharomyces cerevisiae DNA damage and repair pathways and discovered 43% more phosphopeptides than the previous study. PMID:18563926

  2. 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

  3. 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.

  4. Highly accurate retrieval method of Japanese document images through a combination of morphological analysis and OCR

    NASA Astrophysics Data System (ADS)

    Katsuyama, Yutaka; Takebe, Hiroaki; Kurokawa, Koji; Saitoh, Takahiro; Naoi, Satoshi

    2001-12-01

    We have developed a method that allows Japanese document images to be retrieved more accurately by using OCR character candidate information and a conventional plain text search engine. In this method, the document image is first recognized by normal OCR to produce text. Keyword areas are then estimated from the normal OCR produced text through morphological analysis. A lattice of candidate- character codes is extracted from these areas, and then character strings are extracted from the lattice using a word-matching method in noun areas and a K-th DP-matching method in undefined word areas. Finally, these extracted character strings are added to the normal OCR produced text to improve document retrieval accuracy when u sing a conventional plain text search engine. Experimental results from searches of 49 OHP sheet images revealed that our method has a high recall rate of 98.2%, compared to 90.3% with a conventional method using only normal OCR produced text, while requiring about the same processing time as normal OCR.

  5. Fast and Accurate Radiative Transfer Calculations Using Principal Component Analysis for Climate Modeling

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

    Radiative transfer (RT) computations are an essential component of energy budget calculations in climate models. However, full treatment of RT processes is computationally expensive, prompting usage of 2-stream approximations in operational climate models. This simplification introduces errors of the order of 10% in the top of the atmosphere (TOA) fluxes [Randles 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 simulations. 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. Here, we extend 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. Comparisons between the new model, called Universal Principal Component Analysis model for Radiative Transfer (UPCART), 2-stream models (such as those used in climate applications) and line-by-line RT models are performed, in order for spectral radiances, spectral fluxes and broadband fluxes. Each of these are calculated at the TOA for several scenarios with varying aerosol types, extinction and scattering optical depth profiles, and solar and viewing geometries. We demonstrate that very accurate radiative forcing estimates can be obtained, with better than 1% accuracy in all spectral regions and better than 0.1% in most cases as compared to an exact line-by-line RT model. The model is comparable in speeds to 2-stream models, potentially rendering UPCART useful for operational General Circulation Models (GCMs). The operational speed and accuracy of UPCART can be further

  6. 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.

  7. 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

  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. PMID:25577004

  9. 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

  10. Thermodynamic Analysis of Isotope Effects on Triple Points and/or Melting Temperatures

    NASA Astrophysics Data System (ADS)

    Van Hook, W. Alexander

    1995-05-01

    Available literature information on triple point or melting point isotope effects (and related physical properties) is subjected to thermodynamic analysis and consistency checks. New values for the melting point isotope effects for C6H6/CgD6 and c-C6H12/c-C6D12 are reported. 6Li/7Li melting point isotope effects reported recently by Hidaka and Lunden (Z. Naturforsch. 49 a, 475 (1994)) for various inorganic salts are questioned

  11. 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)

  12. 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.

  13. Contaminant source apportionment by PIMMS lead isotope analysis and SEM-image analysis.

    PubMed

    McGill, R A; Pearce, J M; Fortey, N J; Watt, J; Ault, L; Parrish, R R

    2003-03-01

    By combining scanning electron microscopy (SEM) image analysis and laser ablation plasma ionisation multi-collector mass spectrometry (LA-PIMMS), high precision lead isotope analyses can be obtained from individual metal-rich particles. Soils from Wolverhampton and Nottingham were sampled on the basis of high Pb concentrations or brownfield location. Pressed powder pellets of each were rastered by LA-PIMMS to obtain a bulk Pb-isotope signature. The results plot along an apparent mixing line between the major sources of lead contamination in the UK, that is UK ore deposits and alkyl-lead from petrol additives (Australian ore). Two particularly lead-rich soils were chosen to investigate the lead distribution and isotope variability between size and density fractions. The fine-grained and low-density fractions contained most of the lead and have Pb-isotope ratios comparable with the bulk soils. By contrast, the small, lead-enriched denser fractions contained only a minor proportion of the total lead but Pb-isotope signatures indicating relative enrichment in one or other of the end-members from the mixing line. Further characterisation of individual Pb-rich grains is in progress. PMID:12901075

  14. 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

  15. 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

  16. 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

  17. 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...

  18. An accurate modeling, simulation, and analysis tool for predicting and estimating Raman LIDAR system performance

    NASA Astrophysics Data System (ADS)

    Grasso, Robert J.; Russo, Leonard P.; Barrett, John L.; Odhner, Jefferson E.; Egbert, Paul I.

    2007-09-01

    BAE Systems presents the results of a program to model the performance of Raman LIDAR systems for the remote detection of atmospheric gases, air polluting hydrocarbons, chemical and biological weapons, and other molecular species of interest. Our model, which integrates remote Raman spectroscopy, 2D and 3D LADAR, and USAF atmospheric propagation codes permits accurate determination of the performance of a Raman LIDAR system. The very high predictive performance accuracy of our model is due to the very accurate calculation of the differential scattering cross section for the specie of interest at user selected wavelengths. We show excellent correlation of our calculated cross section data, used in our model, with experimental data obtained from both laboratory measurements and the published literature. In addition, the use of standard USAF atmospheric models provides very accurate determination of the atmospheric extinction at both the excitation and Raman shifted wavelengths.

  19. 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

  20. 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

  1. 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.

  2. Spent fuel temperature and age determination from the analysis of uranium and plutonium isotopics

    SciTech Connect

    Scott, Mark R; Eccleston, George W; Bedell, Jeffrey J; Lockard, Chanelle M

    2009-01-01

    The capability to determine the age (time since irradiation) of spent fuel can be useful for verification and safeguards. While the age of spent fuel can be determined based on measurements of short-lived fission products, these measurements are not routinely done nor generally reported. As an alternative, age can also be determined if the uranium (U) and plutonium (Pu) isotopic values are available. Uranium isotopics are not strongly affected by fuel temperature, and bumup is determined from the {sup 235}U and {sup 236}U isotopic values. Age is calculated after estimating the {sup 241}Pu at the end of irradiation while accounting for the fuel temperature, which is determined from {sup 239}Pu or {sup 240}Pu. Burnup and age determinations are calibrated to reactor models that provide uranium and plutonium isotopics over the range of fuel irradiation. The reactor model must contain sufficient fidelity on details of the reactor type, fuel burnup, irradiation history, initial fuel enrichment and fuel temperature to obtain accurate isotopic calculations. If the latter four are unknown, they can be derived from the uranium and plutonium isotopics. Fuel temperature has a significant affect on the production of plutonium isotopics; therefore, one group cross section reactor models, such as ORIGEN, cannot be used for these calculations. Multi-group cross section set codes, such as Oak Ridge National Laboratory's TRITON code, must be used.

  3. 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

  4. Detailed assessment of isotope ratio infrared spectroscopy and isotope ratio mass spectrometry for the stable isotope analysis of plant and soil waters

    NASA Astrophysics Data System (ADS)

    Zhao, L.; Xiao, H.; Zhou, J.; Wang, L.; Cheng, G.; Zhou, M.; Yin, L.; McCabe, M. F.

    2011-12-01

    As an alternative to isotope ratio mass spectrometry (IRMS) the isotope ratio infrared spectroscopy (IRIS) approach has the advantage of low cost, continuous measurement and capacity for field based application for the analysis of stable water isotopes. Recent studies have indicated that there are potential issues of organic contamination of the spectral signal in the IRIS method, resulting in errant readings for leaf samples. To gain a more thorough understanding of the effects of sample type (e.g., leaf, root, stem and soil), sample species, sampling time and climatic condition (dry vs. wet) on water isotope estimates using IRIS, we collected soil samples and plant components from a number of major species at a fine temporal resolution (every two hours for 24-48 hours) across three locations with different climatic conditions in the Heihe River Basin, China. The hydrogen and oxygen isotopic composition of the extracted water from these samples was measured using both an IRMS and IRIS instrument. Results show that the mean discrepancy between the IRMS and IRIS approach, for δ18O and δD respectively, was: -5.6% and -75.7% for leaf water; -4.0% and -23.3% for stem water; -3.4% and -28.2% for root water; -6.7% and -0.5% for xylem water; -0.06% and -0.3% for xylem flow; and -0.1% and 0.3% for soil water. The order of the discrepancy followed: leaf > stem ≈ root > xylem > xylem flow ≈ soil. In general, species of the same functional types (e.g., woody vs. herbaceous) within similar habitats showed similar deviations. For different functional types, the differences were large. Sampling during the nighttime did not remove the observed deviations.

  5. Detailed assessment of isotope ratio infrared spectroscopy and isotope ratio mass spectrometry for the stable isotope analysis of plant and soil waters.

    PubMed

    Zhao, Liangju; Xiao, Honglang; Zhou, Jian; Wang, Lixin; Cheng, Guodong; Zhou, Maoxian; Yin, Li; McCabe, Matthew F

    2011-10-30

    As an alternative to isotope ratio mass spectrometry (IRMS), the isotope ratio infrared spectroscopy (IRIS) approach has the advantage of low cost, continuous measurement and the capacity for field-based application for the analysis of the stable isotopes of water. Recent studies have indicated that there are potential issues of organic contamination of the spectral signal in the IRIS method, resulting in incorrect results for leaf samples. To gain a more thorough understanding of the effects of sample type (e.g., leaf, root, stem and soil), sample species, sampling time and climatic condition (dry vs. wet) on water isotope estimates using IRIS, we collected soil samples and plant components from a number of major species at a fine temporal resolution (every 2 h for 24-48 h) across three locations with different climatic conditions in the Heihe River Basin, China. The hydrogen and oxygen isotopic compositions of the extracted water from these samples were measured using both an IRMS and an IRIS instrument. The results show that the mean discrepancies between the IRMS and IRIS approaches for δ(18) O and δD, respectively, were: -5.6‰ and -75.7‰ for leaf water; -4.0‰ and -23.3‰ for stem water; -3.4‰ and -28.2‰ for root water; -0.5‰ and -6.7‰ for xylem water; -0.06‰ and -0.3‰ for xylem flow; and -0.1‰ and 0.3‰ for soil water. The order of the discrepancy was: leaf > stem ≈ root > xylem > xylem flow ≈ soil. In general, species of the same functional types (e.g., woody vs. herbaceous) within similar habitats showed similar deviations. For different functional types, the differences were large. Sampling at nighttime did not remove the observed deviations. PMID:21953962

  6. Microbeam titanium isotopic analysis by resonance ionization mass spectrometry

    SciTech Connect

    Spiegel, D.R.; Davis, A.M.; Clayton, R.N. . Enrico Fermi Inst.); Pellin, M.J.; Calaway, W.F.; Burnett, J.W.; Coon, S.R.; Young, C.E.; Gruen, D.M. )

    1991-01-01

    The importance of isotopic anomalies in refractory inclusions in meteorites is well established. Measurements of the anomalies using conventional mass spectrometry are often rendered difficult, however, by isobarically interfering isotopes: for example, {sup 48}Ti and {sup 48}Ca. Resonance ionization mass spectrometry (RIMS) can substantially reduce isobaric interferences in a number of systems. We have employed RIMS for the in situ detection of Ti atoms sputtered from pure Ti metal and from several terrestrial oxides containing both Ti and Ca. Tunable lasers were employed to resonantly ionize neutral Ti atoms. We have chosen Ti specifically because of the importance of Ti isotopic anomalies in cosmochemistry.

  7. Further analysis of the IRIS iron isotope experiment

    NASA Technical Reports Server (NTRS)

    Tarle, G.; Ahlen, S. P.; Cartwright, B. G.; Solarz, M.

    1980-01-01

    The IRIS Fe isotope experiment was extended to atomic charges of Z = 19, with isotopic distributions for 500 events ranging from 18 to 28. Normalization of the detector response functions at Fe-56 produced a single well resolved peak at Sc-45, establishing the resolution and mass scale of the device over the entire charge region. The abundance distributions for the predominantly primary isotopes Ca-40, Fe-54, Fe-56, Ni-58, and Ni-60 do not indicate a large admixture of material with distinctly nonsolar abundances.

  8. Isotopomer Spectral Analysis: Utilizing Nonlinear Models in Isotopic Flux Studies.

    PubMed

    Kelleher, Joanne K; Nickol, Gary B

    2015-01-01

    We present the principles underlying the isotopomer spectral analysis (ISA) method for evaluating biosynthesis using stable isotopes. ISA addresses a classic conundrum encountered in the use of radioisotopes to estimate biosynthesis rates whereby the information available is insufficient to estimate biosynthesis. ISA overcomes this difficulty capitalizing on the additional information available from the mass isotopomer labeling profile of a polymer. ISA utilizes nonlinear regression to estimate the two unknown parameters of the model. A key parameter estimated by ISA represents the fractional contribution of the tracer to the precursor pool for the biosynthesis, D. By estimating D in cells synthesizing lipids, ISA quantifies the relative importance of two distinct pathways for flux of glutamine to lipid, reductive carboxylation, and glutaminolysis. ISA can also evaluate the competition between different metabolites, such as glucose and acetoacetate, as precursors for lipogenesis and thereby reveal regulatory properties of the biosynthesis pathway. The model is flexible and may be expanded to quantify sterol biosynthesis allowing tracer to enter the pathway at three different positions, acetyl CoA, acetoacetyl CoA, and mevalonate. The nonlinear properties of ISA provide a method of testing for the presence of gradients of precursor enrichment illustrated by in vivo sterol synthesis. A second ISA parameter provides the fraction of the polymer that is newly synthesized over the time course of the experiment. In summary, ISA is a flexible framework for developing models of polymerization biosynthesis providing insight into pools and pathway that are not easily quantified by other techniques. PMID:26358909

  9. 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.

  10. 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.

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

    PubMed Central

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

    2013-01-01

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

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

    PubMed

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

    2013-05-01

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

  13. Uncertainty analysis of densities and isotopics: Handling correlations

    SciTech Connect

    Favorite, J. A.; Armstrong, J. C.; Burr, T.

    2013-07-01

    This paper discusses two cases of correlated parameters in uncertainty analyses: (1) the case of measured mass, density, and volume or spatial dimension correlations; and (2) the case of measured material isotopics, where increasing one atom fraction must cause the others to decrease. In the first case, an equation is derived that has a term due to uncertain density, a term due to uncertain dimensions, and a term due to the correlation between density and dimensions. In a numerical test problem, this equation gives the same result as the standard equation that treats mass and dimensions independently. In the case of isotopics, an equation is derived relating the uncertainty due to uncertain isotopic fractions to the sensitivities to isotopic densities, which are easier to calculate. The equation is verified in a test problem. (authors)

  14. 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)

  15. 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.

  16. 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

  17. 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

  18. 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.

  19. Accurate and semi-automated analysis of bacterial association with mammalian cells.

    PubMed

    Murphy, C M; Paré, S; Galea, G; Simpson, J C; Smith, S G J

    2016-03-01

    To efficiently and accurately quantify the interactions of bacteria with mammalian cells, a reliable fluorescence microscopy assay was developed. Bacteria were engineered to become rapidly and stably fluorescent using Green Fluorescent Protein (GFP) expressed from an inducible Tet promoter. Upon application of the fluorescent bacteria onto a monolayer, extracellular bacteria could be discriminated from intracellular bacteria by antibody staining and microscopy. All bacteria could be detected by GFP expression. External bacteria stained orange, whereas internalised bacteria did not. Internalised bacteria could thus be discriminated from external bacteria by virtue of being green but not orange fluorescent. Image acquisition and counting of various fluorophore-stained entities were accomplished with a high-content screening platform. This allowed for semi-automated and accurate counting of intracellular and extracellular bacteria. PMID:26769557

  20. 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.

  1. 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.

  2. PC/FRAM plutonium isotopic analysis of CdTe gamma-ray spectra

    NASA Astrophysics Data System (ADS)

    Vo, D. T.; Russo, P. A.

    2002-07-01

    This paper reports the results of isotopics measurements of plutonium with the new CdTe gamma-ray spectrometer. These are the first wide-range plutonium gamma-ray isotopics analysis results obtained with other than germanium spectrometers. The CdTe spectrometer measured small plutonium reference samples in reasonable count times, covering the range from low to high burnup. The complete experimental hardware included the new, commercial, portable CdTe detector and two commercial portable multichannel analyzers. Version 4 of FRAM is the software that performed the isotopics analysis.

  3. Origin and Fate of Organic Compounds in Water: Characterization by Compound-Specific Stable Isotope Analysis

    NASA Astrophysics Data System (ADS)

    Schmidt, Torsten C.; Jochmann, Maik A.

    2012-07-01

    Within the past 15 years, compound-specific stable isotope analysis has continued to increase in popularity in the area of contaminant hydrology of organic molecules. In particular, in cases where concentration data alone are insufficient to elucidate environmental processes unequivocally, the isotope signature can provide additional unique information. Specifically, it can help answer questions about contaminant source apportionment, quantification of biotic and abiotic processes, and identification of transformation reactions on a mechanistic level. We review advances in laboratory and field investigations and exemplary applications in contaminant hydrology via stable isotope analysis. We also highlight future directions in the field.

  4. 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. PMID:26716730

  5. Stable isotope dietary analysis of the Tianyuan 1 early modern human

    PubMed Central

    Hu, Yaowu; Shang, Hong; Tong, Haowen; Nehlich, Olaf; Liu, Wu; Zhao, Chaohong; Yu, Jincheng; Wang, Changsui; Trinkaus, Erik; Richards, Michael P.

    2009-01-01

    We report here on the isotopic analysis of the diet of one of the oldest modern humans found in Eurasia, the Tianyuan 1 early modern human dating to ≈40,000 calendar years ago from Tianyuan Cave (Tianyuandong) in the Zhoukoudian region of China. Carbon and nitrogen isotope analysis of the human and associated faunal remains indicate a diet high in animal protein, and the high nitrogen isotope values suggest the consumption of freshwater fish. To confirm this inference, we measured the sulfur isotope values of terrestrial and freshwater animals around the Zhoukoudian area and of the Tianyuan 1 human, which also support the interpretation of a substantial portion of the diet from freshwater fish. This analysis provides the direct evidence for the consumption of aquatic resources by early modern humans in China and has implications for early modern human subsistence and demography. PMID:19581579

  6. 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.

  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. Forensic utility of isotope ratio analysis of the explosive urea nitrate and its precursors.

    PubMed

    Aranda, Roman; Stern, Libby A; Dietz, Marianne E; McCormick, Meghan C; Barrow, Jason A; Mothershead, Robert F

    2011-03-20

    Urea nitrate (UN) is an improvised explosive made from readily available materials. The carbon and nitrogen isotope composition of UN and its component ions, urea and nitrate, could aid in a forensic investigation. A method was developed to separate UN into its component ions for δ(15)N measurements by dissolving the sample with KOH, drying the sample, followed by removal of the urea by dissolution into 100% methanol. UN was synthesized to assess for preservation of the carbon and nitrogen isotope compositions of reactants (urea and nitric acid) and product UN. Based on nitrogen isotope mass balance, all UN samples contained varying amounts of excess nitric acid, making the ionic separation an essential step in the nitrogen isotope analysis. During UN synthesis experiments, isotopic composition of the reactants is preserved in the product UN, but the urea in the product UN is slightly enriched in (15)N (<1‰) relative to the reactant urea. Published isotopic compositions of UN reactants, urea and nitric acid, have large ranges (urea δ(15)N = -10.8 to +3.3‰; urea δ(13)C = -18.2 to -50.6‰; and nitric acid δ(15)N = -1.8 to +4.0‰). The preservation of isotopic composition of reactants in UN, along with a significant variability in isotopic composition of reactants, indicates that isotope ratio analysis may be used to test if urea or nitric acid collected during an investigation is a possible reactant for a specific UN sample. The carbon and nitrogen isotope ratios differ significantly between two field-collected UN samples, as well as the lab-synthesized UN samples. These observed variations suggest that this approach is useful for discriminating between materials which are otherwise chemically identical. PMID:20729019

  9. 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

  10. 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

  11. Achieving accurate nuetron-multiplicity analysis of metals and oxides with weighted point model equations.

    SciTech Connect

    Burward-Hoy, J. M.; Geist, W. H.; Krick, M. S.; Mayo, D. R.

    2004-01-01

    Neutron multiplicity counting is a technique for the rapid, nondestructive measurement of plutonium mass in pure and impure materials. This technique is very powerful because it uses the measured coincidence count rates to determine the sample mass without requiring a set of representative standards for calibration. Interpreting measured singles, doubles, and triples count rates using the three-parameter standard point model accurately determines plutonium mass, neutron multiplication, and the ratio of ({alpha},n) to spontaneous-fission neutrons (alpha) for oxides of moderate mass. However, underlying standard point model assumptions - including constant neutron energy and constant multiplication throughout the sample - cause significant biases for the mass, multiplication, and alpha in measurements of metal and large, dense oxides.

  12. Accurate Structure Prediction and Conformational Analysis of Cyclic Peptides with Residue-Specific Force Fields.

    PubMed

    Geng, Hao; Jiang, Fan; Wu, Yun-Dong

    2016-05-19

    Cyclic peptides (CPs) are promising candidates for drugs, chemical biology tools, and self-assembling nanomaterials. However, the development of reliable and accurate computational methods for their structure prediction has been challenging. Here, 20 all-trans CPs of 5-12 residues selected from Cambridge Structure Database have been simulated using replica-exchange molecular dynamics with four different force fields. Our recently developed residue-specific force fields RSFF1 and RSFF2 can correctly identify the crystal-like conformations of more than half CPs as the most populated conformation. The RSFF2 performs the best, which consistently predicts the crystal structures of 17 out of 20 CPs with rmsd < 1.1 Å. We also compared the backbone (ϕ, ψ) sampling of residues in CPs with those in short linear peptides and in globular proteins. In general, unlike linear peptides, CPs have local conformational free energies and entropies quite similar to globular proteins. PMID:27128113

  13. 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. PMID:23870940

  14. 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.

  15. Monitoring and evaluation of dechlorination processes using compound-specific chlorine isotope analysis.

    PubMed

    Sakaguchi-Söder, Kaori; Jager, Johannes; Grund, Harald; Matthäus, Felix; Schüth, Christoph

    2007-01-01

    A simple, quick and sensitive method for the compound-specific stable chlorine isotope analysis of chlorinated solvents by conventional quadrupole gas chromatography/mass spectrometry (GC/MS) is presented. With this method, compound-specific stable chlorine isotope ratios of typical chlorinated solvents like tetrachloroethene (PCE) and trichloroethene (TCE) can be determined quantitatively within 30 min by direct injection. The chlorine isotope ratios of target substances are calculated from the peak areas of several selected molecular ions and fragment ions of the substances, using a set of unique mathematical equations. The precision of the method was demonstrated through reproducibility tests. An internal precision of +/-0.4 per thousand to +/-1.1 per thousand was obtained when analyzing PCE and TCE in the 10-1000 pmol range. The validity of the method was further demonstrated by determining the chlorine isotopic fractionation factor during the reductive dechlorination of TCE in a batch experiment using zero-valent iron. The chlorine isotopic fractionation factor was calculated as 0.9976 +/- 0.0011 with a correlation coefficient of 0.9469 (n = 38). The high correlation coefficient indicates that compound-specific stable chlorine isotope analysis can be performed with sufficient accuracy using conventional quadrupole GC/MS when significant fractionation takes place during a reaction. For the first time, the chlorine isotope fractionation factor of TCE during an abiotic anaerobic dechlorination process was determined using quadrupole GC/MS, without offline sample preparation. PMID:17705345

  16. 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

  17. 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

  18. 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.

  19. Headspace analysis: A new application for isotopic characterization of dissolved organic contaminants

    SciTech Connect

    Slater, G.F.; Dempster, H.S.; Lollar, B.S.; Ahad, J.

    1999-01-01

    Petroleum products and industrial solvents are among the most ubiquitous contaminants of soil and groundwater and the source of several common and hazardous volatile organic chemicals (VOCs). Volatilization is a key determinant of the fate of VOCs in the subsurface environment, impacting contaminant partitioning between the aqueous, gaseous, and nonaqueous liquid phases. This study uses stable carbon isotope analysis to investigate the isotopic effects involved in volatilization of trichloroethylene (TCE) and toluene from both free product (or pure phase) and aqueous solutions. Results indicate that, during volatilization from the aqueous phase and from free product, the isotopic composition of TCE and toluene remains unchanged within reproducibility limits. These results have two important implications for contaminant hydrogeology. First, they suggest that carbon isotopic signatures may be useful in tracing contaminant transport between the vapor, aqueous, and NAPL phases since they remain conservative during phase changes. Second, they demonstrate the utility of headspace extraction (sampling of the vapor phase or headspace above an aqueous solution) as a preparatory technique for isotopic analysis of dissolved VOCs. Headspace isotopic analysis provides a straightforward and rapid technique for {delta}{sup 13}C analysis of dissolved organic contaminants at concentrations as low as hundreds of ppb.

  20. 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...

  1. 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...

  2. Systematic analysis of reaction cross sections of carbon isotopes

    SciTech Connect

    Horiuchi, W.; Suzuki, Y.; Abu-Ibrahim, B.; Kohama, A.

    2007-04-15

    We systematically analyze total reaction cross sections of carbon isotopes with N= 6-16 on a {sup 12}C target for wide range of incident energy. The intrinsic structure of the carbon isotope is described by a Slater determinant generated from a phenomenological mean-field potential, which reasonably well reproduces the ground-state properties for most of the even N isotopes. We need separate studies not only for odd nuclei but also for {sup 16}C and {sup 22}C to improve their wave functions. The density of the carbon isotope is constructed by eliminating the effect of the center-of-mass motion. For the calculations of the cross sections, we take two schemes, the Glauber approximation and the eikonal model using a global optical potential. Both the reaction models successfully reproduce low and high incident energy data on the cross sections of {sup 12}C, {sup 13}C, and {sup 16}C on {sup 12}C. The calculated reaction cross sections of {sup 15}C are found to be considerably smaller than the empirical values observed at low energy. We find a consistent parametrization of the nucleon-nucleon scattering amplitude, differently from previous ones. Finally, we predict the total reaction cross section of {sup 22}C on {sup 12}C.

  3. Is the Meta-Analysis of Correlation Coefficients Accurate When Population Correlations Vary?

    ERIC Educational Resources Information Center

    Field, Andy P.

    2005-01-01

    One conceptualization of meta-analysis is that studies within the meta-analysis are sampled from populations with mean effect sizes that vary (random-effects models). The consequences of not applying such models and the comparison of different methods have been hotly debated. A Monte Carlo study compared the efficacy of Hedges and Vevea's…

  4. 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.

  5. 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

  6. 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

  7. 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.

  8. TOPICA: an accurate and efficient numerical tool for analysis and design of ICRF antennas

    NASA Astrophysics Data System (ADS)

    Lancellotti, V.; Milanesio, D.; Maggiora, R.; Vecchi, G.; Kyrytsya, V.

    2006-07-01

    The demand for a predictive tool to help in designing ion-cyclotron radio frequency (ICRF) antenna systems for today's fusion experiments has driven the development of codes such as ICANT, RANT3D, and the early development of TOPICA (TOrino Polytechnic Ion Cyclotron Antenna) code. This paper describes the substantive evolution of TOPICA formulation and implementation that presently allow it to handle the actual geometry of ICRF antennas (with curved, solid straps, a general-shape housing, Faraday screen, etc) as well as an accurate plasma description, accounting for density and temperature profiles and finite Larmor radius effects. The antenna is assumed to be housed in a recess-like enclosure. Both goals have been attained by formally separating the problem into two parts: the vacuum region around the antenna and the plasma region inside the toroidal chamber. Field continuity and boundary conditions allow formulating of a set of two coupled integral equations for the unknown equivalent (current) sources; then the equations are reduced to a linear system by a method of moments solution scheme employing 2D finite elements defined over a 3D non-planar surface triangular-cell mesh. In the vacuum region calculations are done in the spatial (configuration) domain, whereas in the plasma region a spectral (wavenumber) representation of fields and currents is adopted, thus permitting a description of the plasma by a surface impedance matrix. Owing to this approach, any plasma model can be used in principle, and at present the FELICE code has been employed. The natural outcomes of TOPICA are the induced currents on the conductors (antenna, housing, etc) and the electric field in front of the plasma, whence the antenna circuit parameters (impedance/scattering matrices), the radiated power and the fields (at locations other than the chamber aperture) are then obtained. An accurate model of the feeding coaxial lines is also included. The theoretical model and its TOPICA

  9. 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

  10. 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.

  11. 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.

  12. TOPLHA: an accurate and efficient numerical tool for analysis and design of LH antennas

    NASA Astrophysics Data System (ADS)

    Milanesio, D.; Lancellotti, V.; Meneghini, O.; Maggiora, R.; Vecchi, G.; Bilato, R.

    2007-09-01

    Auxiliary ICRF heating systems in tokamaks often involve large complex antennas, made up of several conducting straps hosted in distinct cavities that open towards the plasma. The same holds especially true in the LH regime, wherein the antennas are comprised of arrays of many phased waveguides. Upon observing that the various cavities or waveguides couple to each other only through the EM fields existing over the plasma-facing apertures, we self-consistently formulated the EM problem by a convenient set of multiple coupled integral equations. Subsequent application of the Method of Moments yields a highly sparse algebraic system; therefore formal inversion of the system matrix happens to be not so memory demanding, despite the number of unknowns may be quite large (typically 105 or so). The overall strategy has been implemented in an enhanced version of TOPICA (Torino Polytechnic Ion Cyclotron Antenna) and in a newly developed code named TOPLHA (Torino Polytechnic Lower Hybrid Antenna). Both are simulation and prediction tools for plasma facing antennas that incorporate commercial-grade 3D graphic interfaces along with an accurate description of the plasma. In this work we present the new proposed formulation along with examples of application to real life large LH antenna systems.

  13. 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

  14. 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

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

    PubMed

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

    2013-05-01

    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

  16. Fast and accurate single-cell RNA-seq analysis by clustering of transcript-compatibility counts.

    PubMed

    Ntranos, Vasilis; Kamath, Govinda M; Zhang, Jesse M; Pachter, Lior; Tse, David N

    2016-01-01

    Current approaches to single-cell transcriptomic analysis are computationally intensive and require assay-specific modeling, which limits their scope and generality. We propose a novel method that compares and clusters cells based on their transcript-compatibility read counts rather than on the transcript or gene quantifications used in standard analysis pipelines. In the reanalysis of two landmark yet disparate single-cell RNA-seq datasets, we show that our method is up to two orders of magnitude faster than previous approaches, provides accurate and in some cases improved results, and is directly applicable to data from a wide variety of assays. PMID:27230763

  17. Nd and Hf isotopic analysis of Barberton komatiites

    NASA Astrophysics Data System (ADS)

    Robin, Christophe; Blichert-Toft, Janne; Arndt, Nicholas; Wilson, Allan; Byerly, Gary

    2013-04-01

    In order to constrain the origin of komatiites from the Barberton Belt, particularly the nature of their mantle source and the conditions of partial melting, we analyzed the Nd and Hf isotopic compositions of 33 komatiite samples. Of these 15 were from the ca. 3.5 Ga Komati Formation, 3 were from the 3.47 Ga Hooggenoeg Fm and 15 from the 3.3 Ga Weltevreden Fm. The samples were collected from outcrop and represent the three main types of komatiite found in the Barberton Belt: i.e. Al-depleted, Al-undepleted and Al-enriched. The analyses were carried out at ENS Lyon using the procedure described by Blichert-Toft et al. For each sample suite we obtained a relatively large range of calculated initial isotopic values. In each suite, one or more samples gave an unreasonably high or low value, particularly for the Hf isotopic system. Excluding these outliers, the values are as follows: Komati Fm, epsilon Nd = -0.8 to +2.5, epsilon Hf = +1 to +8; Hooggenoeg Fm, epsilon Nd = -0.1 to +0.2, epsilon Hf = +1 to +2; Weltevreden Fm, epsilon Nd = 0.3 to +2.0, epsilon Hf = +4 to +13. There were no systematic differences between the isotopic compositions of the three different types of komatiite. Within the relatively large variability of the data, the epsilon Hf values tend to become more positive with age while the epsilon Nd values remain essentially constant. These results are broadly in line with those obtained in most of the previous studies of Barberton komatiites. Notably: 1) there is a wide range in initial isotopic compositions that is not compatible with normal magmatic processes. At least part of the range can be attributed to disturbance, particularly of the Lu-Hf system, after eruption of the lavas; 2) notwithstanding this uncertainty, both the Nd and Hf isotopic compositions are slightly radiogenic, indicating formation from a moderately depleted mantle source. To obtain more reliable data, we intend a) to analyse carefully chosen and prepared samples from core

  18. An accurate nonlinear finite element analysis and test correlation of a stiffened composite wing panel

    NASA Technical Reports Server (NTRS)

    Davis, D. D., Jr.; Krishnamurthy, T.; Stroud, W. J.; Mccleary, S. L.

    1991-01-01

    State-of-the-art nonlinear finite element analysis techniques are evaluated by applying them to a realistic aircraft structural component. A wing panel from the V-22 tiltrotor aircraft is chosen because it is a typical modern aircraft structural component for which there is experimental data for comparison of results. From blueprints and drawings, a very detailed finite element model containing 2284 9-node Assumed Natural-Coordinate Strain elements was generated. A novel solution strategy which accounts for geometric nonlinearity through the use of corotating element reference frames and nonlinear strain-displacement relations is used to analyze this detailed model. Results from linear analyses using the same finite element model are presented in order to illustrate the advantages and costs of the nonlinear analysis as compared with the more traditional linear analysis.

  19. 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.

  20. NREL's Field Data Repository Supports Accurate Home Energy Analysis (Fact Sheet)

    SciTech Connect

    None, None

    2012-02-01

    This fact sheet discusses NREL's work to develop a repository of research-level residential building characteristics and historical energy use data to support ongoing efforts to improve the accuracy of residential energy analysis tools and the efficiency of energy assessment processes. The objective of this project is to create a robust empirical data source to support the research goals of the Department of Energy's Building America program, which is to improve the efficiency of existing U.S. homes by 30% to 50%. Researchers can use this data source to test the accuracy of building energy simulation software and energy audit procedures, ultimately leading to more credible and less expensive energy analysis.

  1. Liquid chromatography combined with mass spectrometry for 13C isotopic analysis in life science research.

    PubMed

    Godin, Jean-Philippe; Fay, Laurent-Bernard; Hopfgartner, Gérard

    2007-01-01

    Among the different disciplines covered by mass spectrometry, measurement of (13)C/(12)C isotopic ratio crosses a large section of disciplines from a tool revealing the origin of compounds to more recent approaches such as metabolomics and proteomics. Isotope ratio mass spectrometry (IRMS) and molecular mass spectrometry (MS) are the two most mature techniques for (13)C isotopic analysis of compounds, respectively, for high and low-isotopic precision. For the sample introduction, the coupling of gas chromatography (GC) to either IRMS or MS is state of the art technique for targeted isotopic analysis of volatile analytes. However, liquid chromatography (LC) also needs to be considered as a tool for the sample introduction into IRMS or MS for (13)C isotopic analyses of non-volatile analytes at natural abundance as well as for (13)C-labeled compounds. This review presents the past and the current processes used to perform (13)C isotopic analysis in combination with LC. It gives particular attention to the combination of LC with IRMS which started in the 1990's with the moving wire transport, then subsequently moved to the chemical reaction interface (CRI) and was made commercially available in 2004 with the wet chemical oxidation interface (LC-IRMS). The LC-IRMS method development is also discussed in this review, including the possible approaches for increasing selectivity and efficiency, for example, using a 100% aqueous mobile phase for the LC separation. In addition, applications for measuring (13)C isotopic enrichments using atmospheric pressure LC-MS instruments with a quadrupole, a time-of-flight, and an ion trap analyzer are also discussed as well as a LC-ICPMS using a prototype instrument with two quadrupoles. PMID:17853432

  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. 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.

  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. 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.

  7. 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.

  8. Analysis of isotope and organic carbon signatures in hillslope hydrographs

    NASA Astrophysics Data System (ADS)

    Dusek, Jaromir; Vogel, Tomas; Dohnal, Michal; Jankovec, Jakub; Sanda, Martin; Votrubova, Jana

    2015-04-01

    Headwater catchments are among the most important areas for investigation of isotope and carbon fluxes because their small sizes best enable separation of above- and below ground compartments for improved understanding of the respective transport mechanisms. So far, only few studies utilized stable isotope information in modeling and even fewer linked dissolved carbon fluxes to mixing or transport models. Stable isotopes of water and dissolved organic carbon provide basis for studying transport processes ranging from soil profile scale to hillslope and catchment scale. In this study, stormflow dynamics of oxygen-18 and dissolved organic carbon was analyzed using a physically based modeling approach. One-dimensional dual-continuum vertical flow and transport model, based on Richards and advection-dispersion equations, was used to simulate the subsurface processes during significant rainfall-runoff episodes of a summer season. Water flow and transport of solutes were assumed to take place in two mutually communicating continua, the soil matrix and the network of preferential pathways. Oxygen-18 and dissolved organic carbon were observed in soil water, stormflow discharge in the experimental hillslope trench, and stream discharge at the catchment outlet. In the present study, we analyzed the transformation of input solute signals into signatures observed in the stormflow discharge. The research was supported by the Czech Science Foundation Project No. 14-15201J.

  9. 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.

  10. 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

  11. 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.

  12. 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.

  13. 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.

  14. 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

  15. 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.

  16. Generalized transition state theory calculations for the reactions D+H2 and H+D2 using an accurate potential energy surface: Explanation of the kinetic isotope effect

    NASA Astrophysics Data System (ADS)

    Garrett, Bruce C.; Truhlar, Donald G.

    1980-03-01

    Rate constants are calculated for the reactions D+H2→DH+H and H+D2→HD+D and compared to measured values. An accurate potential energy surface, based on the ab initio calculations of Liu and Siegbahn, was used. Rates were calculated using both conventional transition state theory and canonical variational theory. In the former, the generalized transition state dividing surface is located at the saddle point; in the latter it is located to maximize the generalized free energy of activation. We show that, in the absence of tunneling corrections, locating the generalized-transition-state dividing surface variationally has an important quantitative effect on the predicted rate constants for these systems and that, when tunneling is included, most of the effect of using a better dividing surface can be included in conventional transition state theory for these systems by using a consistent transmission coefficient for quantal scattering by the vibrationally adiabatic potential energy curve. Tunneling effects are important for these reactions even for temperatures larger than 400 K. We show how to separate classical recrossing effects from quantal corrections on reaction-coordinate motion in both the transmission coefficients and the kinetic isotope effects. Our most complete calculations are in excellent agreement with most of the measured rate constants and kinetic isotope effects.

  17. 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.

  18. TOPLHA: an accurate and efficient numerical tool for analysis and design of LH antennas

    NASA Astrophysics Data System (ADS)

    Milanesio, D.; Meneghini, O.; Maggiora, R.; Guadamuz, S.; Hillairet, J.; Lancellotti, V.; Vecchi, G.

    2012-01-01

    This paper presents a self-consistent, integral-equation approach for the analysis of plasma-facing lower hybrid (LH) launchers; the geometry of the waveguide grill structure can be completely arbitrary, including the non-planar mouth of the grill. This work is based on the theoretical approach and code implementation of the TOPICA code, of which it shares the modular structure and constitutes the extension into the LH range. Code results are validated against the literature results and simulations from similar codes.

  19. 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

  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. 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

  2. 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...

  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. PMID:26946933

  4. 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.

  5. Spectrally-accurate algorithm for the analysis of flows in two-dimensional vibrating channels

    NASA Astrophysics Data System (ADS)

    Zandi, S.; Mohammadi, A.; Floryan, J. M.

    2015-11-01

    A spectral algorithm based on the immersed boundary conditions (IBC) concept has been developed for the analysis of flows in channels bounded by vibrating walls. The vibrations take the form of travelling waves of arbitrary profile. The algorithm uses a fixed computational domain with the flow domain immersed in its interior. Boundary conditions enter the algorithm in the form of constraints. The spatial discretization uses a Fourier expansion in the stream-wise direction and a Chebyshev expansion in the wall-normal direction. Use of the Galileo transformation converts the unsteady problem into a steady one. An efficient solver which takes advantage of the structure of the coefficient matrix has been used. It is demonstrated that the method can be extended to more extreme geometries using the overdetermined formulation. Various tests confirm the spectral accuracy of the algorithm.

  6. 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

  7. 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.

  8. 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

  9. 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.

  10. Stable isotope analysis using tunable diode laser spectroscopy

    NASA Technical Reports Server (NTRS)

    Becker, Joseph F.; Sauke, Todd B.; Loewenstein, Max

    1992-01-01

    Ratios of C-12/C-13 in CO2 have been measured using a tunable diode laser (TDL) spectrometer to an accuracy of better than 0.4 percent. These results were made possible by the use of state-of-the-art high-temperature TDLs, an etalon and wavenumber calibration technique, high-speed assembly language controlled data acquisition, and the ratioing of absorbances from simultaneously acquired sample and reference data scans. The dual beam spectrometer that is employed uses the sweep integration technique in a spectral region where adjacent spectral lines are of approximately equal absorbance at the expected isotopic abundances.

  11. 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

  12. 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

  13. Integrative subcellular proteomic analysis allows accurate prediction of human disease-causing genes.

    PubMed

    Zhao, Li; Chen, Yiyun; Bajaj, Amol Onkar; Eblimit, Aiden; Xu, Mingchu; Soens, Zachry T; Wang, Feng; Ge, Zhongqi; Jung, Sung Yun; He, Feng; Li, Yumei; Wensel, Theodore G; Qin, Jun; Chen, Rui

    2016-05-01

    Proteomic profiling on subcellular fractions provides invaluable information regarding both protein abundance and subcellular localization. When integrated with other data sets, it can greatly enhance our ability to predict gene function genome-wide. In this study, we performed a comprehensive proteomic analysis on the light-sensing compartment of photoreceptors called the outer segment (OS). By comparing with the protein profile obtained from the retina tissue depleted of OS, an enrichment score for each protein is calculated to quantify protein subcellular localization, and 84% accuracy is achieved compared with experimental data. By integrating the protein OS enrichment score, the protein abundance, and the retina transcriptome, the probability of a gene playing an essential function in photoreceptor cells is derived with high specificity and sensitivity. As a result, a list of genes that will likely result in human retinal disease when mutated was identified and validated by previous literature and/or animal model studies. Therefore, this new methodology demonstrates the synergy of combining subcellular fractionation proteomics with other omics data sets and is generally applicable to other tissues and diseases. PMID:26912414

  14. 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

  15. SMRT Sequencing for Parallel Analysis of Multiple Targets and Accurate SNP Phasing.

    PubMed

    Guo, Xiaoge; Lehner, Kevin; O'Connell, Karen; Zhang, Jenny; Dave, Sandeep S; Jinks-Robertson, Sue

    2015-12-01

    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

  16. Accurate determination of the diffusion coefficient of proteins by Fourier analysis with whole column imaging detection.

    PubMed

    Zarabadi, Atefeh S; Pawliszyn, Janusz

    2015-02-17

    Analysis in the frequency domain is considered a powerful tool to elicit precise information from spectroscopic signals. In this study, the Fourier transformation technique is employed to determine the diffusion coefficient (D) of a number of proteins in the frequency domain. Analytical approaches are investigated for determination of D from both experimental and data treatment viewpoints. The diffusion process is modeled to calculate diffusion coefficients based on the Fourier transformation solution to Fick's law equation, and its results are compared to time domain results. The simulations characterize optimum spatial and temporal conditions and demonstrate the noise tolerance of the method. The proposed model is validated by its application for the electropherograms from the diffusion path of a set of proteins. Real-time dynamic scanning is conducted to monitor dispersion by employing whole column imaging detection technology in combination with capillary isoelectric focusing (CIEF) and the imaging plug flow (iPF) experiment. These experimental techniques provide different peak shapes, which are utilized to demonstrate the Fourier transformation ability in extracting diffusion coefficients out of irregular shape signals. Experimental results confirmed that the Fourier transformation procedure substantially enhanced the accuracy of the determined values compared to those obtained in the time domain. PMID:25607375

  17. Parents were accurate proxy reporters of urgent pediatric asthma health services—a retrospective agreement analysis

    PubMed Central

    Ungar, Wendy J.; Davidson-Grimwood, Sara R.; Cousins, Martha

    2016-01-01

    Objective To assess agreement between parents’ proxy reports of children’s respiratory-related health service use and administrative data. Study Design and Setting A retrospective analysis of statistical agreement between clinical and claims data for reports of physician visits, emergency department (ED) visits, and hospitalizations in 545 asthmatic children recruited from sites in the greater Toronto area was conducted. Health services use data were extracted from the Ontario Health Insurance Plan and Canadian Institute for Health Information databases for each child for the interval coinciding with the proxy report for each health service type. Results Agreement between administrative data and respondent reports (n =545) was substantial for hospitalizations in the past year (κ =0.80 [0.74, 0.86]), moderate for ED visits in the past year (κ =0.60 [0.53, 0.67]), and slight for physician visits (κ =0.13 [0.00, 0.27]) in the past 6 months. Income, parent’s education, and child quality-of-life symptom scores did not affect agreement. Agreement for ED visits was significantly higher (P <0.05) for children who had an asthma attack in the past 6 months (κ =0.61 [0.54, 0.68]) compared to children who did not (κ =0.25 [0.00, 0.59]). Conclusion Parents of asthmatic children are reliable reporters of their child’s respiratory-related urgent health services utilization. PMID:17938060

  18. [An Accurate Diagnosis is Possible with a Systematic Analysis of Routine Laboratory Data].

    PubMed

    Yonekawa, Osamu

    2015-09-01

    Routine laboratory tests are ordered for almost all in- and outpatients. A systematic analysis of routine laboratory data can give doctors valuable clinical information about patients. In some cases, a correct diag- nosis can be made using laboratory data alone. In our laboratory, we use five processes to evaluate routine laboratory data. Firstly, we estimate the patient's general condition based on A/G, Hb, TP, Alb, ChE, and platelet (PLT) levels. Secondly, we look for inflammation and malignancy based on WBC, CRP, PLT, fibrinogen, and ESR levels and the protein electrophoresis pattern. Thirdly, we examine the major organs, especially the liver and kidney. We check the liver for hepatocyte damage, obstruction, hepatic synthetic function, infection, and malignancy. We estimate GFR and check the kidney for any localized damage. We then check the chemistry, hematology, and immunology. Finally, we form a conclusion after a comprehensive interpretation of the above four processes. With this systematic approach, any members of the laboratory unit can easily estimate the exact pathological status of the patient. In this case study, marked change of TP indicated non-selective loss from the skin; namely a burn. Tissue injury and infections due to different focuses were the most likely causes of severe inflammation. Neither the liver nor kidney was severely damaged. Continual bleeding and hemolysis through the clinical course probably caused anemia. Hypooxygenic respiratory failure and metabolic alkalosis were confirmed by blood gasses. Multiple organ failure was suggested. PMID:26731896

  19. 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. PMID:20597895

  20. 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

  1. Stable isotope fractionation analysis as a tool to monitor biodegradation in contaminated acquifers

    NASA Astrophysics Data System (ADS)

    Meckenstock, Rainer U.; Morasch, Barbara; Griebler, Christian; Richnow, Hans H.

    2004-12-01

    The assessment of biodegradation in contaminated aquifers has become an issue of increasing importance in the recent years. To some extent, this can be related to the acceptance of intrinsic bioremediation or monitored natural attenuation as a means to manage contaminated sites. Among the few existing methods to detect biodegradation in the subsurface, stable isotope fractionation analysis (SIFA) is one of the most promising approaches which is pronounced by the drastically increasing number of applications. This review covers the recent laboratory and field studies assessing biodegradation of contaminants via stable isotope analysis. Stable isotope enrichment factors have been found that vary from no fractionation for dioxygenase reactions converting aromatic hydrocarbons over moderate fractionation by monooxygenase reactions ( ɛ=-3‰) and some anaerobic studies on microbial degradation of aromatic hydrocarbons ( ɛ=-1.7‰) to larger fractionations by anaerobic dehalogenation reactions of chlorinated solvents ( ɛ=between -5‰ and -30‰). The different isotope enrichment factors can be related to the respective biochemical reactions. Based on that knowledge, we discuss under what circumstances SIFA can be used for a qualitative or even a quantitative assessment of biodegradation in the environment. In a steadily increasing number of cases, it was possible to explain biodegradation processes in the field based on isotope enrichment factors obtained from laboratory experiments with pure cultures and measured isotope values from the field. The review will focus on the aerobic and anaerobic degradation of aromatic hydrocarbons and chlorinated solvents as the major contaminants of groundwater. Advances in the instrumental development for stable isotope analysis are only mentioned if it is important for the understanding of the application.

  2. Growth versus metabolic tissue replacement in mouse tissues determined by stable carbon and nitrogen isotope analysis

    NASA Astrophysics Data System (ADS)

    Macavoy, S. E.; Jamil, T.; Macko, S. A.; Arneson, L. S.

    2003-12-01

    Stable isotope analysis is becoming an extensively used tool in animal ecology. The isotopes most commonly used for analysis in terrestrial systems are those of carbon and nitrogen, due to differential carbon fractionation in C3 and C4 plants, and the approximately 3‰ enrichment in 15N per trophic level. Although isotope signatures in animal tissues presumably reflect the local food web, analysis is often complicated by differential nutrient routing and fractionation by tissues, and by the possibility that large organisms are not in isotopic equilibrium with the foods available in their immediate environment. Additionally, the rate at which organisms incorporate the isotope signature of a food through both growth and metabolic tissue replacement is largely unknown. In this study we have assessed the rate of carbon and nitrogen isotopic turnover in liver, muscle and blood in mice following a diet change. By determining growth rates, we were able to determine the proportion of tissue turnover caused by growth versus that caused by metabolic tissue replacement. Growth was found to account for approximately 10% of observed tissue turnover in sexually mature mice (Mus musculus). Blood carbon was found to have the shortest half-life (16.9 days), followed by muscle (24.7 days). Liver carbon turnover was not as well described by the exponential decay equations as other tissues. However, substantial liver carbon turnover was observed by the 28th day after diet switch. Surprisingly, these tissues primarily reflect the carbon signature of the protein, rather than carbohydrate, source in their diet. The nitrogen signature in all tissues was enriched by 3 - 5‰ over their dietary protein source, depending on tissue type, and the isotopic turnover rates were comparable to those observed in carbon.

  3. Whole-Genome Sequencing Analysis Accurately Predicts Antimicrobial Resistance Phenotypes in Campylobacter spp.

    PubMed

    Zhao, S; Tyson, G H; Chen, Y; Li, C; Mukherjee, S; Young, S; Lam, C; Folster, J P; Whichard, J M; McDermott, P F

    2016-01-01

    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

  4. 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. PMID:24128481

  5. 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.

  6. 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

  7. 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

  8. An automated method for analysis of microcirculation videos for accurate assessment of tissue perfusion

    PubMed Central

    2012-01-01

    Background Imaging of the human microcirculation in real-time has the potential to detect injuries and illnesses that disturb the microcirculation at earlier stages and may improve the efficacy of resuscitation. Despite advanced imaging techniques to monitor the microcirculation, there are currently no tools for the near real-time analysis of the videos produced by these imaging systems. An automated system tool that can extract microvasculature information and monitor changes in tissue perfusion quantitatively might be invaluable as a diagnostic and therapeutic endpoint for resuscitation. Methods The experimental algorithm automatically extracts microvascular network and quantitatively measures changes in the microcirculation. There are two main parts in the algorithm: video processing and vessel segmentation. Microcirculatory videos are first stabilized in a video processing step to remove motion artifacts. In the vessel segmentation process, the microvascular network is extracted using multiple level thresholding and pixel verification techniques. Threshold levels are selected using histogram information of a set of training video recordings. Pixel-by-pixel differences are calculated throughout the frames to identify active blood vessels and capillaries with flow. Results Sublingual microcirculatory videos are recorded from anesthetized swine at baseline and during hemorrhage using a hand-held Side-stream Dark Field (SDF) imaging device to track changes in the microvasculature during hemorrhage. Automatically segmented vessels in the recordings are analyzed visually and the functional capillary density (FCD) values calculated by the algorithm are compared for both health baseline and hemorrhagic conditions. These results were compared to independently made FCD measurements using a well-known semi-automated method. Results of the fully automated algorithm demonstrated a significant decrease of FCD values. Similar, but more variable FCD values were calculated

  9. 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

  10. 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

  11. 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.

  12. Asymptotic Analysis of Time-Dependent Neutron Transport Coupled with Isotopic Depletion and Radioactive Decay

    SciTech Connect

    Brantley, P S

    2006-09-27

    We describe an asymptotic analysis of the coupled nonlinear system of equations describing time-dependent three-dimensional monoenergetic neutron transport and isotopic depletion and radioactive decay. The classic asymptotic diffusion scaling of Larsen and Keller [1], along with a consistent small scaling of the terms describing the radioactive decay of isotopes, is applied to this coupled nonlinear system of equations in a medium of specified initial isotopic composition. The analysis demonstrates that to leading order the neutron transport equation limits to the standard time-dependent neutron diffusion equation with macroscopic cross sections whose number densities are determined by the standard system of ordinary differential equations, the so-called Bateman equations, describing the temporal evolution of the nuclide number densities.

  13. [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

  14. Investigation of Nebular Processes Through Oxygen Isotopic Analysis of Primitive Meteorite Materials

    NASA Technical Reports Server (NTRS)

    Leshin, Laurie

    2002-01-01

    As a direct result of support provided by this grant, precise and accurate determination of delta(18)O and delta(17)O in silicates (and other minerals) by ion microprobe (both IMS 6f and IMS 1270) are now being carried out in several laboratories, and these analyses, combined with application of laser fluorination techniques, have led to a proliferation of oxygen isotopic data in the past approx. 3 years. The applications of these techniques in cosmochemical research have been myriad, from understanding the most refractory objects in the nebula (CAIs) to the low temperature alteration processes on meteorite parent bodies. Here, we describe our progress in understanding the oxygen isotopic microdistributions in primitive meteorite materials, as directly supported by this Origins grant.

  15. 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.

  16. Nutritional assessment by isotope dilution analysis of body composition

    SciTech Connect

    Szeluga, D.J.; Stuart, R.K.; Utermohlen, V.; Santos, G.W.

    1984-10-01

    The three components of body mass, body cell mass (BCM), extracellular fluid (ECF), and fat + extracellular solids (ECS: bone, tendon, etc) can be quantified using established isotope dilution techniques. With these techniques, total body water (TBW) and ECF are measured using 3H/sub 2/O and /sup 82/Bromine, respectively, as tracers. BCM is calculated from intracellular fluid (ICF) where ICF . TBW - ECF. Fat + ECS is estimated as: body weight - (BCM + ECF). TBW and ECF can be determined by either of two calculation methods, one requiring several timed plasma samples (extrapolation method) and one requiring a single plasma sample and a 4-h urine collection (urine-corrected method). The comparability of the two calculation methods was evaluated in 20 studies in 12 bone marrow transplant recipients. We found that for determination of TBW and ECF there was a very strong linear relationship (r2 greater than 0.98) between the calculation methods. Further comparisons (by t test, 2-sided) indicated that for the determination of ECF, the methods were not significantly (p greater than 0.90) different; however, TBW determined by the urine-corrected method was slightly (0.1 to 6%), but significantly (p less than 0.01) greater than that determined by the extrapolation method. Therefore, relative to the extrapolation method, the urine-corrected method ''over-estimates'' BCM and ''under-estimates'' fat + ECS since determination of these compartment sizes depends on measurement of TBW. We currently use serial isotope dilution studies to monitor the body composition changes of patients receiving therapeutic nutritional support.

  17. 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.

  18. 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.

  19. In-cloud sulfate addition to single particles resolved with sulfur isotope analysis during HCCT-2010

    NASA Astrophysics Data System (ADS)

    Harris, E.; Sinha, B.; van Pinxteren, D.; Schneider, J.; Poulain, L.; Collett, J.; D'Anna, B.; Fahlbusch, B.; Foley, S.; Fomba, K. W.; George, C.; Gnauk, T.; Henning, S.; Lee, T.; Mertes, S.; Roth, A.; Stratmann, F.; Borrmann, S.; Hoppe, P.; Herrmann, H.

    2014-01-01

    In-cloud production of sulfate modifies the aerosol size distribution, with important implications for the magnitude of indirect and direct aerosol cooling and the impact of SO2 emissions on the environment. We investigate which sulfate sources dominate the in-cloud addition of sulfate to different particle classes as an air parcel passes through an orographic cloud. Sulfate aerosol, SO2 and H2SO4 were collected upwind, in-cloud and downwind of an orographic cloud for three cloud measurement events during the Hill Cap Cloud Thuringia campaign in Autumn, 2010 (HCCT-2010). Combined SEM and NanoSIMS analysis of single particles allowed the δ34S of particulate sulfate to be resolved for particle size and type. The most important in-cloud SO2 oxidation pathway at HCCT-2010 was aqueous oxidation catalysed by transition metal ions (TMI catalysis), which was shown with single particle isotope analyses to occur primarily in cloud droplets nucleated on coarse mineral dust. In contrast, direct uptake of H2SO4(g) and ultrafine particulate were the most important sources modifying fine mineral dust, increasing its hygroscopicity and facilitating activation. Sulfate addition to "mixed" particles (secondary organic and inorganic aerosol) and coated soot was dominated by in-cloud aqueous SO2 oxidation by H2O2 and direct uptake of H2SO4(g) and ultrafine particle sulfate, depending on particle size mode and time of day. These results provide new insight into in-cloud sulfate production mechanisms, and show the importance of single particle measurements and models to accurately assess the environmental effects of cloud processing.

  20. In-cloud sulfate addition to single particles resolved with sulfur isotope analysis during HCCT-2010

    NASA Astrophysics Data System (ADS)

    Harris, E.; Sinha, B.; van Pinxteren, D.; Schneider, J.; Poulain, L.; Collett, J.; D'Anna, B.; Fahlbusch, B.; Foley, S.; Fomba, K. W.; George, C.; Gnauk, T.; Henning, S.; Lee, T.; Mertes, S.; Roth, A.; Stratmann, F.; Borrmann, S.; Hoppe, P.; Herrmann, H.

    2014-04-01

    In-cloud production of sulfate modifies aerosol size distribution, with important implications for the magnitude of indirect and direct aerosol cooling and the impact of SO2 emissions on the environment. We investigate which sulfate sources dominate the in-cloud addition of sulfate to different particle classes as an air parcel passes through an orographic cloud. Sulfate aerosol, SO2 and H2SO4 were collected upwind, in-cloud and downwind of an orographic cloud for three cloud measurement events during the Hill Cap Cloud Thuringia campaign in autumn 2010 (HCCT-2010). Combined SEM and NanoSIMS analysis of single particles allowed the δ34S of particulate sulfate to be resolved for particle size and type. The most important in-cloud SO2 oxidation pathway at HCCT-2010 was aqueous oxidation catalysed by transition metal ions (TMI catalysis), which was shown with single particle isotope analyses to occur primarily in cloud droplets nucleated on coarse mineral dust. In contrast, direct uptake of H2SO4 (g) and ultrafine particulate were the most important sources modifying fine mineral dust, increasing its hygroscopicity and facilitating activation. Sulfate addition to "mixed" particles (secondary organic and inorganic aerosol) and coated soot was dominated by in-cloud aqueous SO2 oxidation by H2O2 and direct uptake of H2SO4 (g) and ultrafine particle sulfate, depending on particle size mode and time of day. These results provide new insight into in-cloud sulfate production mechanisms, and show the importance of single particle measurements and models to accurately assess the environmental effects of cloud processing.

  1. 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.

  2. 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

  3. 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

  4. 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.

  5. 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

  6. 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

    2016-01-01

    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

  7. 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

  8. Degradation of reactive dyes in wastewater from the textile industry by ozone: analysis of the products by accurate masses.

    PubMed

    Constapel, Marc; Schellenträger, Marc; Marzinkowski, Joachim Michael; Gäb, Siegmar

    2009-02-01

    The present work describes the use of ozone to degrade selected reactive dyes from the textile industry and the analysis of the resulting complex mixture by liquid chromatography/mass spectrometry (LC-MS). To allow certain identification of the substances detected in the wastewater, the original dyes were also investigated either separately or in a synthetic mixture of three dyes (trichromie). Since the reactive dyes are hydrolyzed during the dyeing process, procedures for the hydrolysis were worked out first for the individual dyes. The ozonated solutions were concentrated by solid-phase extraction, which separated very polar or ionic substances from moderately polar degradation products. The latter, which are the primary degradation products, were investigated by liquid chromatography/mass spectrometry with a tandem quadrupole time-of-flight mass analyzer. Accurate masses, which in most cases could be determined with a deviation of accurate masses, UV-vis spectra and, of course, knowledge of the structures of the original dyes, plausible structures could be proposed for most of the components of the moderately polar fraction. These structures were confirmed by 1H NMR in cases where it was practical to isolate the degradation products by preparative HPLC. PMID:19110293

  9. 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. PMID:22940042

  10. 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‰. PMID:25647449

  11. 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.

  12. 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

  13. 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

  14. 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...

  15. 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.

  16. 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 ...

  17. GRPAUT: a program for Pu isotopic analysis (a user's guide). ISPO task A. 76

    SciTech Connect

    Fleissner, J G

    1981-01-30

    GRPAUT is a modular program for performing automated Pu isotopic analysis supplied to the International Atomic Energy Agency (IAEA) per ISPO Task A.76. Section I of this user's guide for GRPAUT presents an overview of the various programs and disk files that are used in performing a Pu isotopic analysis. Section II describes the program GRFEDT which is used in creating and editing the analysis parameter file that contains all the spectroscopic information needed at runtime by GRPAUT. An example of the dialog and output of GRFEDT is shown in Appendix B. Section III describes the operation of the various GRPAUT modules: GRPNL2, the peak stripping module; EFFCH2, the efficiency calculation module; and ISOAUT, the isotopic calculation module. (A description of the peak fitting methodology employed by GRPNL2 is presented in Appendix A.) Finally, Section IV outlines the procedure for determining the peak shape constants for a detector system and describes the operation of the program used to create and edit the peak shape parameter files. An output of GRPAUT, showing an example of a complete isotopic analysis, is presented in Appendix C. Source listings of all the Fortran programs supplied to the Agency under ISPO Task A.76 are contained in Appendix E.

  18. 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…

  19. 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...

  20. 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 ...

  1. A new method of accurate broken rotor bar diagnosis based on modulation signal bispectrum analysis of motor current signals

    NASA Astrophysics Data System (ADS)

    Gu, F.; Wang, T.; Alwodai, A.; Tian, X.; Shao, Y.; Ball, A. D.

    2015-01-01

    Motor current signature analysis (MCSA) has been an effective way of monitoring electrical machines for many years. However, inadequate accuracy in diagnosing incipient broken rotor bars (BRB) has motivated many studies into improving this method. In this paper a modulation signal bispectrum (MSB) analysis is applied to motor currents from different broken bar cases and a new MSB based sideband estimator (MSB-SE) and sideband amplitude estimator are introduced for obtaining the amplitude at (1 ± 2 s)fs (s is the rotor slip and fs is the fundamental supply frequency) with high accuracy. As the MSB-SE has a good performance of noise suppression, the new estimator produces more accurate results in predicting the number of BRB, compared with conventional power spectrum analysis. Moreover, the paper has also developed an improved model for motor current signals under rotor fault conditions and an effective method to decouple the BRB current which interferes with that of speed oscillations associated with BRB. These provide theoretical supports for the new estimators and clarify the issues in using conventional bispectrum analysis.

  2. How accurate are polymer models in the analysis of Förster resonance energy transfer experiments on proteins?

    NASA Astrophysics Data System (ADS)

    O'Brien, Edward P.; Morrison, Greg; Brooks, Bernard R.; Thirumalai, D.

    2009-03-01

    Single molecule Förster resonance energy transfer (FRET) experiments are used to infer the properties of the denatured state ensemble (DSE) of proteins. From the measured average FRET efficiency, ⟨E⟩, the distance distribution P(R ) is inferred by assuming that the DSE can be described as a polymer. The single parameter in the appropriate polymer model (Gaussian chain, wormlike chain, or self-avoiding walk) for P(R ) is determined by equating the calculated and measured ⟨E⟩. In order to assess the accuracy of this "standard procedure," we consider the generalized Rouse model (GRM), whose properties [⟨E⟩ and P(R )] can be analytically computed, and the Molecular Transfer Model for protein L for which accurate simulations can be carried out as a function of guanadinium hydrochloride (GdmCl) concentration. Using the precisely computed ⟨E⟩ for the GRM and protein L, we infer P(R ) using the standard procedure. We find that the mean end-to-end distance can be accurately inferred (less than 10% relative error) using ⟨E⟩ and polymer models for P(R ). However, the value extracted for the radius of gyration (Rg) and the persistence length (lp) are less accurate. For protein L, the errors in the inferred properties increase as the GdmCl concentration increases for all polymer models. The relative error in the inferred Rg and lp, with respect to the exact values, can be as large as 25% at the highest GdmCl concentration. We propose a self-consistency test, requiring measurements of ⟨E⟩ by attaching dyes to different residues in the protein, to assess the validity of describing DSE using the Gaussian model. Application of the self-consistency test to the GRM shows that even for this simple model, which exhibits an order→disorder transition, the Gaussian P(R ) is inadequate. Analysis of experimental data of FRET efficiencies with dyes at several locations for the cold shock protein, and simulations results for protein L, for which accurate FRET

  3. 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

  4. 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.

  5. 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

  6. 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

  7. 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.

  8. 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.

  9. 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.

  10. 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. PMID:22088068

  11. 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

  12. Scanning-electron-microscope image processing for accurate analysis of line-edge and line-width roughness

    NASA Astrophysics Data System (ADS)

    Hiraiwa, Atsushi; Nishida, Akio

    2012-03-01

    The control of line-edge or line-width roughness (LER/LWR) is a challenge especially for future devices that are fabricated using extreme-ultraviolet lithography. Accurate analysis of the LER/LWR plays an essential role in this challenge and requires the noise involved in scanning-electron-microscope (SEM) images to be reduced by appropriate image processing prior to analyses. In order to achieve this, the authors simulated SEM images using the Monte-Carlo method and detected line edges in experimental and these theoretical images after noise filtering using new imageanalysis software. The validity of these simulation and software was confirmed by a good agreement between the experimental and theoretical results. In the case when the image pixels aligned perpendicular (crosswise) to line edges were averaged, the variance var(φ) that was additionally induced by the image noise decreased with the number NPIX,X of averaged pixels but turned to increase for relatively large NPIX,X's. Real LER/LWR, however, remained unaffected. On the other hand, averaging image pixels aligned parallel (longitudinal) to line edges not only reduced var(φ) but smoothed the real LER/LWR. As a result, the nominal variance of the real LWR, obtained using simple arithmetic, monotonically decreased with the number NPIX,L of averaged pixels. Artifactual oscillations were additionally observed in power spectral densities. var(φ) in this case decreased in an inverse proportion to the square root of NPIX,L according to the statistical mechanism clarified here. In this way, image processing has a marked effect on the LER/LWR analysis and needs to be much more cared and appropriately applied. All the aforementioned results not only constitute a solid basis of but improve previous empirical instructions for accurate analyses. The most important instruction is to avoid the longitudinal averaging and to crosswise average an optimized number of image pixels consulting the equation derived in this

  13. The utilization of stable isotope analysis for the estimation of the geographic origins of unidentified cadavers.

    PubMed

    McLean, Stuart J; Ikegaya, Hiroshi; Saukko, Pekka J; Zheng, Huang Yung; Itoh, Kyoko; Fushiki, Shinji

    2014-12-01

    The number of unidentified cadavers is increasing worldwide and the effective methods which reveal their geographic origin are not well known. This study reports on the utilization of δ(18)O, δ(13)C, δ(2)H and δ(15)N ratios gained through stable isotope analysis of urine samples collected from eight locations: Chiba, Japan; Fuzhou, China; and Denpasar, Indonesia in our pilot study with data from healthy volunteers from five further locations from healthy volunteers: Melbourne and Perth, Australia; Qingdao, China; Turku, Finland and Oklahoma, USA. This study posits that the utilization of δ(18)O and δ(2)H is more feasible than δ(13)C and δ(15)N stable isotope ratios in differentiating or estimating the origin of human samples. Secondly, this study demonstrated that the δ(18)O and δ(2)H stable isotope ratios of urine samples from eight locations differed significantly. PMID:25447173

  14. 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

  15. High-throughput isotopic analysis of RNA microarrays to quantify microbial resource use

    PubMed Central

    Mayali, Xavier; Weber, Peter K; Brodie, Eoin L; Mabery, Shalini; Hoeprich, Paul D; Pett-Ridge, Jennifer

    2012-01-01

    Most microorganisms remain uncultivated, and typically their ecological roles must be inferred from diversity and genomic studies. To directly measure functional roles of uncultivated microbes, we developed Chip-stable isotope probing (SIP), a high-sensitivity, high-throughput SIP method performed on a phylogenetic microarray (chip). This approach consists of microbial community incubations with isotopically labeled substrates, hybridization of the extracted community rRNA to a microarray and measurement of isotope incorporation—and therefore substrate use—by secondary ion mass spectrometer imaging (NanoSIMS). Laboratory experiments demonstrated that Chip-SIP can detect isotopic enrichment of 0.5 atom % 13C and 0.1 atom % 15N, thus permitting experiments with short incubation times and low substrate concentrations. We applied Chip-SIP analysis to a natural estuarine community and quantified amino acid, nucleic acid or fatty acid incorporation by 81 distinct microbial taxa, thus demonstrating that resource partitioning occurs with relatively simple organic substrates. The Chip-SIP approach expands the repertoire of stable isotope-enabled methods available to microbial ecologists and provides a means to test genomics-generated hypotheses about biogeochemical function in any natural environment. PMID:22158395

  16. 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

  17. Stable isotope analysis of organic carbon in small (µg C) samples and dissolved organic matter using a GasBench preparation device.

    PubMed

    Lang, Susan Q; Bernasconi, Stefano M; Früh-Green, Gretchen L

    2012-01-15

    The stable isotopes of organic matter can provide valuable information on carbon cycling dynamics, microbial metabolisms, and past climates. Since bulk measurements may mask dynamic changes to critical portions of the organic pool, researchers are increasingly isolating individual compounds for isotopic analysis. The amount of carbon isolated is frequently small, requiring specialized equipment for its analysis. We present a simple and accurate method to measure the δ(13)C values of µg-amounts of organic compounds and dissolved organic matter in freshwaters using wet oxidation and a GasBench II preparation device. Samples containing 3 µg C can be analyzed with a precision of <0.4‰. For samples containing 1.2 µg C, the precision is <0.8‰. The blank is estimated to be ~0.2 µg C. The accuracy of the method is demonstrated for a wide range of compounds including those that are difficult to oxidize such as humic acid and phthalic acid. The δ(13)C values of DOC from river and riparian ground water determined by this method are comparable with those determined with an elemental analyzer on freeze-dried samples of DOC. The low detection limit and the ease with which it can be combined with isolation techniques such as liquid chromatography make this technique attractive for the off-line analysis of organic compounds, and open new possibilities for the development of methodologies for compound-specific carbon isotope analysis of complex mixtures separated by HPLC. PMID:22215572

  18. 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

  19. 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.

  20. 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.

  1. 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

  2. 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

  3. Noise filtering of scanning-electron-microscope images for accurate analysis of line-edge and line-width roughness

    NASA Astrophysics Data System (ADS)

    Hiraiwa, Atsushi; Nishida, Akio

    2012-10-01

    The control of line-edge or line-width roughness (LER/LWR) is a challenge, especially for future devices that are fabricated using extreme-ultraviolet (EUV) lithography. Accurate analysis of the LER/LWR plays an essential role in this challenge and requires the noise involved in scanning-electron-microscope (SEM) images to be reduced by appropriate noise filtering prior to analysis. To achieve this, we simulated the SEM images using a Monte Carlo method, and detected line edges in both experimental and theoretical images after noise filtering using new image-analysis software. The validity of this software and these simulations was confirmed by a good agreement between the experimental and theoretical results. In the case when the image pixels aligned perpendicular (crosswise) to line edges were averaged, the variance var(φ) that was additionally induced by the image noise decreased with a number N of averaged pixels, with exceptions when N was relatively large, whereupon the variance increased. The optimal N to minimize var(φ) was formulated based on a statistical mechanism of this change. LER/LWR statistics estimated using the crosswise filtering remained unaffected when N was smaller than the aforementioned optimal value, but monotonically changed when N was larger contrary to expectations. This change was possibly caused by an asymmetric scan-signal profile at edges. On the other hand, averaging image pixels aligned parallel (longitudinal) to line edges not only reduced var(φ) but smoothed real LER/LWR. As a result, the nominal variance of real LWR, obtained using simple arithmetic, monotonically decreased with a number N of averaged pixels. Artifactual oscillations were additionally observed in power spectral densities. Var(φ) in this case decreased in inverse proportion to the square root of N according to the statistical mechanism clarified here. In this way, the noise filtering has a marked effect on the LER/LWR analysis and needs to be appropriately

  4. Molecular Formula Identification Using Isotope Pattern Analysis and Calculation of Fragmentation Trees

    PubMed Central

    Dührkop, Kai; Hufsky, Franziska; Böcker, Sebastian

    2014-01-01

    We present the results of a fully automated de novo approach for identification of molecular formulas in the CASMI 2013 contest. Only results for Category 1 (molecular formula identification) were submitted. Our approach combines isotope pattern analysis and fragmentation pattern analysis and is completely independent from any (spectral and structural) database. We correctly identified the molecular formula for ten out of twelve challenges, being the best automated method competing in this category. PMID:26819880

  5. 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

  6. 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.

  7. Detection of 1,N(2)-propano-2'-deoxyguanosine in human urine by stable isotope dilution UHPLC-MS/MS analysis.

    PubMed

    Zhang, Ning; Song, Yuanyuan; Zhang, Weibing; Wang, Hailin

    2016-06-15

    A sensitive and accurate stable isotope dilution UHPLC-MS/MS method was developed and validated for the detection and quantification of ProdG adducts in human urine, a surrogate for the ProdG adducts in genomic DNA of human. A specific solid phase extraction (SPE) approach was established for selective enrichment of urinary ProdG adducts and elimination of urinary matrix facilitating the coupled MS/MS detection. The recovery of the method is estimated about 84.8-107.2%, and the precision are about 0.8-3.6% for intraday and 2.8-10.0% for interday. Due to that the matrix effect is efficiently eliminated by SPE pretreatment, the limits of detection (LODs, S/N=3) and quantification (LOQs, S/N=10) are decreased to 100 and 300 amol for urinary ProdG adducts, respectively. By coupling the developed SPE pretreatment with the UHPLC-MS/MS analysis, ProdG adducts were accurately quantified in healthy human urine. PMID:27158096

  8. Spatially resolved δ13C analysis using laser ablation isotope ratio mass spectrometry

    NASA Astrophysics Data System (ADS)

    Moran, J.; Riha, K. M.; Nims, M. K.; Linley, T. J.; Hess, N. J.; Nico, P. S.

    2014-12-01

    Inherent geochemical, organic matter, and microbial heterogeneity over small spatial scales can complicate studies of carbon dynamics through soils. Stable isotope analysis has a strong history of helping track substrate turnover, delineate rhizosphere activity zones, and identifying transitions in vegetation cover, but most traditional isotope approaches are limited in spatial resolution by a combination of physical separation techniques (manual dissection) and IRMS instrument sensitivity. We coupled laser ablation sampling with isotope measurement via IRMS to enable spatially resolved analysis over solid surfaces. Once a targeted sample region is ablated the resulting particulates are entrained in a helium carrier gas and passed through a combustion reactor where carbon is converted to CO2. Cyrotrapping of the resulting CO2 enables a reduction in carrier gas flow which improves overall measurement sensitivity versus traditional, high flow sample introduction. Currently we are performing sample analysis at 50 μm resolution, require 65 ng C per analysis, and achieve measurement precision consistent with other continuous flow techniques. We will discuss applications of the laser ablation IRMS (LA-IRMS) system to microbial communities and fish ecology studies to demonstrate the merits of this technique and how similar analytical approaches can be transitioned to soil systems. Preliminary efforts at analyzing soil samples will be used to highlight strengths and limitations of the LA-IRMS approach, paying particular attention to sample preparation requirements, spatial resolution, sample analysis time, and the types of questions most conducive to analysis via LA-IRMS.

  9. 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

  10. Compound-Specific Carbon and Hydrogen Isotope Analysis - Field Evidence of MTBE Bioremediation

    NASA Astrophysics Data System (ADS)

    Kuder, T.; Kolhatkar, R. V.; Philp, P.; Wilson, J. T.; Landmeyer, J. E.; Allen, J.

    2002-12-01

    Compound-specific stable isotope analysis allows opportunity to determine the isotopic ratios of individual contaminants. The technique has been applied to confirm biodegradation in studies of chlorinated solvents and recently BTEX, MTBE and TBA. Chemical reactions (including bio- and inorganic degradation) tend to favor molecules with the lighter isotopic species (e.g., 12C, 1H), resulting with enrichment of the unreacted substrate in the heavier isotopic species (13C, D), referred to as kinetic isotopic fractionation, so that the extent of fractionation may be used as a proxy for biodegradation. Processes such as volatilization, sorption etc., result in minimal degree of fractionation and do not interfere with the isotopic signal due to biodegradation. The results presented here show the first successful applications of compound-specific isotope analysis to understanding MTBE biodegradation in the field, at both aerobic and anaerobic sites. Observed fractionations suggest that two different biodegradation pathways may be involved. At a number of anaerobic locations major fractionation effects were observed for both C and H; enrichment factors Ÿnfor both elements were approaching or exceeding -10. A laboratory microcosm study using an enrichment culture yielded similar results (C data only). A characteristic feature of these sites was the presence of high concentrations of TBA. Conversely, at a number of sites, the C composition remained stable with little fractionation and stayed within the analytical precision range or changed minimally, while H displayed significant fractionation in excess of 60 per mil. Moderate agreement of the data with Rayleigh fractionation model was observed, suggesting that biodegradation effect was distorted by variability at the source or the plume was not homogeneous. The enrichment factor calculated for these data is similar to the one Ÿnpublished for aerobic microcosm of MTBE-degrading culture from Vandenberg AFB by Gray et al

  11. 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

  12. 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.

  13. 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

  14. 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

  15. Investigating microbial carbon cycling using natural abundance isotope analysis of PLFA

    NASA Astrophysics Data System (ADS)

    Slater, G. G.; Brady, A.; Cowie, B.

    2008-12-01

    Understanding microbial carbon sources and cycling is fundamental to our conceptualization of microbial ecosystems and their role in biogeochemical cycling in natural systems. Achieving this understanding requires application of a wide range of approaches. Natural abundance isotope analysis of individual compounds, particularly cellular components such as Phospholipids Fatty Acids (PLFA) can provide insights into the carbon sources and metabolic activities of the in situ microbial community from environmental samples. This is primarily because specific PLFA can be well resolved by gas chromatography even from complex matrices where confounding biological/organic compound abound. These PLFA can then be attributed to the viable microbial community, in some cases to specific components of this community and due to characteristic biosynthetic fractionations of stable isotope ratios, δ13C analysis of PLFA can: differentiate isotopically distinct primary carbon sources of heterotrophic communities; identify isotopic patterns characteristic of autotrophic versus heterotrophic processes; and elucidate microbial biosynthetic pathways. In cases where there δ13C cannot provide resolution of carbon sources, new approaches in Δ14C of PLFA can be applied. The vast range in Δ14C of ancient and modern carbon provides an easily traceable signal that can differentiate uptake and utilization of these carbon sources. This is particularly useful in cases such as contaminated sites where petroleum based contamination has occurred, or in natural systems where microbial communities may be utilizing geologic versus recently photosynthetically fixed carbon. This talk will present several examples demonstrating the utility of this approach.

  16. 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.

  17. 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.

  18. IsoWeb: A Bayesian Isotope Mixing Model for Diet Analysis of the Whole Food Web

    PubMed Central

    Kadoya, Taku; Osada, Yutaka; Takimoto, Gaku

    2012-01-01

    Quantitative description of food webs provides fundamental information for the understanding of population, community, and ecosystem dynamics. Recently, stable isotope mixing models have been widely used to quantify dietary proportions of different food resources to a focal consumer. Here we propose a novel mixing model (IsoWeb) that estimates diet proportions of all consumers in a food web based on stable isotope information. IsoWeb requires a topological description of a food web, and stable isotope signatures of all consumers and resources in the web. A merit of IsoWeb is that it takes into account variation in trophic enrichment factors among different consumer-resource links. Sensitivity analysis using realistic hypothetical food webs suggests that IsoWeb is applicable to a wide variety of food webs differing in the number of species, connectance, sample size, and data variability. Sensitivity analysis based on real topological webs showed that IsoWeb can allow for a certain level of topological uncertainty in target food webs, including erroneously assuming false links, omission of existent links and species, and trophic aggregation into trophospecies. Moreover, using an illustrative application to a real food web, we demonstrated that IsoWeb can compare the plausibility of different candidate topologies for a focal web. These results suggest that IsoWeb provides a powerful tool to analyze food-web structure from stable isotope data. We provide R and BUGS codes to aid efficient applications of IsoWeb. PMID:22848427

  19. 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

  20. 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

  1. Unified and Isomer-Specific NMR Metabolomics Database for the Accurate Analysis of 13C–1H HSQC Spectra

    PubMed Central

    2015-01-01

    A new metabolomics database and query algorithm for the analysis of 13C–1H HSQC spectra is introduced, which unifies NMR spectroscopic information on 555 metabolites from both the Biological Magnetic Resonance Data Bank (BMRB) and Human Metabolome Database (HMDB). The new database, termed Complex Mixture Analysis by NMR (COLMAR) 13C–1H HSQC database, can be queried via an interactive, easy to use web interface at http://spin.ccic.ohio-state.edu/index.php/hsqc/index. Our new HSQC database separately treats slowly exchanging isomers that belong to the same metabolite, which permits improved query in cases where lowly populated isomers are below the HSQC detection limit. The performance of our new database and query web server compares favorably with the one of existing web servers, especially for spectra of samples of high complexity, including metabolite mixtures from the model organisms Drosophila melanogaster and Escherichia coli. For such samples, our web server has on average a 37% higher accuracy (true positive rate) and a 82% lower false positive rate, which makes it a useful tool for the rapid and accurate identification of metabolites from 13C–1H HSQC spectra at natural abundance. This information can be combined and validated with NMR data from 2D TOCSY-type spectra that provide connectivity information not present in HSQC spectra. PMID:25333826

  2. Unified and isomer-specific NMR metabolomics database for the accurate analysis of (13)C-(1)H HSQC spectra.

    PubMed

    Bingol, Kerem; Li, Da-Wei; Bruschweiler-Li, Lei; Cabrera, Oscar A; Megraw, Timothy; Zhang, Fengli; Brüschweiler, Rafael

    2015-02-20

    A new metabolomics database and query algorithm for the analysis of (13)C-(1)H HSQC spectra is introduced, which unifies NMR spectroscopic information on 555 metabolites from both the Biological Magnetic Resonance Data Bank (BMRB) and Human Metabolome Database (HMDB). The new database, termed Complex Mixture Analysis by NMR (COLMAR) (13)C-(1)H HSQC database, can be queried via an interactive, easy to use web interface at http://spin.ccic.ohio-state.edu/index.php/hsqc/index . Our new HSQC database separately treats slowly exchanging isomers that belong to the same metabolite, which permits improved query in cases where lowly populated isomers are below the HSQC detection limit. The performance of our new database and query web server compares favorably with the one of existing web servers, especially for spectra of samples of high complexity, including metabolite mixtures from the model organisms Drosophila melanogaster and Escherichia coli. For such samples, our web server has on average a 37% higher accuracy (true positive rate) and a 82% lower false positive rate, which makes it a useful tool for the rapid and accurate identification of metabolites from (13)C-(1)H HSQC spectra at natural abundance. This information can be combined and validated with NMR data from 2D TOCSY-type spectra that provide connectivity information not present in HSQC spectra. PMID:25333826

  3. 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

  4. Testing the plutonium isotopic analysis code FRAM with various CdTe detectors.

    SciTech Connect

    Vo, Duc T.; Russo, P. A.

    2002-01-01

    The isotopic analysis code Fixed-energy Response-function Analysis with Multiple efficiency (FRAM)1,2 has been proven to successfully analyze plutonium spectra taken with a portable CdTe detector with Peltier cooling, the first results of this kind for a noncryogenic detector.3 These are the first wide-range plutonium gamma-ray isotopics analysis results obtained with other than Ge spectrometers. The CdTe spectrometer measured small plutonium reference samples in reasonable count times, covering the range from low to high burnup. This paper describes further testing of FRAM with two CdTe detectors of different sizes and resolutions using different analog and digital, portable multichannel analyzers (MCAs).

  5. 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

  6. Coordinated Analysis of Isotopic Anomalies in Antarctic Micrometeorites

    NASA Astrophysics Data System (ADS)

    Haenecour, P.; Floss, C.; Wang, A.; Yada, T.

    2014-06-01

    We carry out coordinated analysis (NanoSIMS 50, Auger Nanoprobe, Raman spectroscopy) of presolar grains (silicates, oxides, SiC) and ^15N-enriched carbonaceous matter in fine-grained Antarctic micrometeorites.

  7. Isotope dilution analysis of Se in human blood serum by using high-power nitrogen microwave-induced plasma mass spectrometry coupled with a hydride generation technique.

    PubMed

    Ohata, M; Ichinose, T; Furuta, N; Shinohara, A; Chiba, M

    1998-07-01

    To establish a method for sensitive, accurate, and precise determination of Se in real samples, isotope dilution analysis using high-power nitrogen microwave-induced plasma mass spectrometry (N2 MIP-IDMS) was conducted. In this study, freeze-dried human blood serum (Standard Reference Material, NIES No. 4) provided by NIES (National Institute for Environmental Studies) was used as a real sample. The measured isotopes of Se were 78Se and 80Se which are the major isotopes of Se. The appropriate amount of a Se spike solution was theoretically calculated by using an error multiplication factor (F) and was confirmed experimentally for the isotope dilution analysis. The mass discrimination effect was corrected for by using a standard Se solution for the measurement of Se isotope ratios in the spiked sample. However, the sensitivity for the detection of Se was not so good and the precision of the determination was not improved (2-3%) by N2 MIP-IDMS with use of the conventional nebulizer. Therefore, a hydride generation system was connected to N2 MIP-IDMS as a sample introduction system (HG-N2 MIP-IDMS) in order to establish a more sensitive detection and a more precise determination of Se. A detection limit (3 sigma) of 10 pg mL-1 could be achieved, and the RSD was less than 1% at the concentration level of 5.0-10.0 ng mL-1 by HG-N2 MIP-IDMS. The analytical results were found to be in a good agreement with those obtained by the standard addition method using conventional Ar ICPMS. PMID:9666737

  8. 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

  9. 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

  10. Quantifying inter-laboratory variability in stable isotope analysis of ancient skeletal remains.

    PubMed

    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

  11. 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.

  12. 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

  13. 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 185ppm/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 5.2ppm) and (54)Cr/(52)Cr (μ(54)Cr* of 13.5ppm) 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

  14. Preservation of terrestrial plant biomarkers from Nachukui Formation sediments and their viability for stable isotope analysis

    NASA Astrophysics Data System (ADS)

    Kahle, E.; Uno, K. T.; Polissar, P. J.; Lepre, C. J.; deMenocal, P. B.

    2013-12-01

    Plio-Pleistocene sedimentary records from the Turkana Basin in eastern Africa provide a unique opportunity to compare a high-resolution record of climate and terrestrial vegetation with important changes in the record of human evolution. Molecular biomarkers from terrestrial vegetation can yield stable isotope ratios of hydrogen and carbon that reflect ancient climate and vegetation. However, the preservation of long-chain plant wax biomarkers in these paleosol, fluvial, and lacustrine sediments is not known, and this preservation must be studied to establish their utility for molecular stable isotope studies. We investigated leaf wax biomarkers in Nachukui Formation sediments deposited between 2.3 and 1.7 Ma to assess biomarker preservation. We analyzed n alkane and n alkanoic acid concentrations and, where suitable, molecular carbon and hydrogen isotope ratios. Molecular abundance distributions show a great deal of variance in biomarker preservation and plant-type source as indicated by the carbon preference index and average chain length. This variation suggests that some samples are suitable for isotopic analysis, while other samples lack primary terrestrial plant biomarker signatures. The biomarker signal in many samples contains significant additional material from unidentified sources. For example, the n-alkane distributions contain an unresolved complex mixture underlying the short and mid-chain n-alkanes. Samples from lacustrine intervals include long-chain diacids, hydroxy acids and (ω-1) ketoacids that suggest degradation of the original acids. Degradation of poorly preserved samples and the addition of non-terrestrial plant biomarkers may originate from a number of processes including forest fire or microbial alteration. Isotopic analysis of well-preserved terrestrial plant biomarkers will be presented along with examples where the original biomarker distribution has been altered.

  15. 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.

  16. 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.

  17. Analysis of Concentrated Uranium Ores Using Stable Isotopes and Elemental Concentrations

    NASA Astrophysics Data System (ADS)

    Miller, D. L.; Riciputi, L. R.; Buerger, S.; Horita, J.; Bostick, D.

    2006-12-01

    The illicit trafficking of nuclear materials presents a continuing threat to national and international security. Various geochemical characteristics of yellowcake (concentrated uranium ore) could potentially provide information on the geologic, geographic, and processing origin of the ore. We have been focusing on investigating the potential of stable isotope analyses, namely carbon, nitrogen, and oxygen, to provide "forensic" information about ore environment and artificial processing methods used to concentrate the uranium ore. Stable isotope analysis of carbon and nitrogen was performed using a Costech elemental analyzer (EA) attached to a Finnigan Mat 252 mass spectrometer. Carbon and nitrogen isotopes can be characteristic of the processing agents used to concentrate the uranium ore. Oxygen analysis was performed using a ThermoFinnigan thermal conversion elemental analyzer (TCEA) attached to a Finnigan Mat 252 mass spectrometer at ORNL. In addition to the stable isotope analyses, elemental concentrations were analyzed using time-of-flight ICP-MS, and uranium isotope composition measured using MC-ICP-MS. Results from a number of yellowcake samples will be presented, illustrating the potential of geochemical characteristics to distinguish among different types of samples. Research sponsored by the Office of Nonproliferation and International Security (NA-24), National Nuclear Security Administration (NNSA), U.S. Department of Energy, under contract DE-AC05-00OR22725 with Oak Ridge National Laboratory, managed and operated by UT-Battelle, LLC. The submitted manuscript has been authored by a contractor of the U.S. Government under contract No. DE- AC05-00OR22725. Accordingly, the U.S. Government retains a nonexclusive, royalty-free license to publish or reproduce the published form of this contribution, or allow others to do so, for U.S. Government purposes.

  18. 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

  19. 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.

  20. 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.

  1. 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.

  2. 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

  3. 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

  4. 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.

  5. 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.

  6. 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

  7. Multi-Isotope Analysis as a Natural Reaction Probe of Biodegradation Mechanisms of 1,2- Dichloroethane

    NASA Astrophysics Data System (ADS)

    Hirschorn, S. K.; Dinglasan-Panlilio, M.; Edwards, E. A.; Lacrampe-Couloume, G.; Sherwood Lollar, B.

    2006-12-01

    1,2-Dichloroethane (1,2-DCA), a chlorinated aliphatic hydrocarbon, is an EPA priority pollutant and a widespread groundwater contaminant. Stable isotope fractionation during biodegradation of 1,2-DCA occurs due to differences in the reaction rates of heavy versus light atoms present at a reacting bond in the 1,2-DCA molecule. In general, light isotopic bonds react more quickly, producing a relative enrichment in the heavy isotope in the remaining contaminant pool. Compound specific isotope analysis has the potential to demonstrate the occurrence and extent of biodegradation at chlorinated solvent contaminated groundwater sites. In this study, stable carbon isotope fractionation was used as a novel reaction probe to provide information about the mechanism of 1,2-DCA biodegradation. Isotopic fractionation was measured during 1,2-DCA degradation by a microbial culture capable of degrading 1,2-DCA under O2-reducing and NO3-reducing conditions. The microbial culture produced isotopic enrichment values that are not only large and reproducible, but are the same whether O2 or NO3 was used as an electron acceptor. The mean isotopic enrichment value of -25.8 permil measured for the microbial culture during 1,2-DCA degradation under both O2 and NO3- reducing conditions can be converted into a kinetic isotope effect (KIE) value to relate the observed isotopic fractionation to the mechanism of degradation. This KIE value (1.05) is consistent with degradation via a hydrolysis (SN2) reaction under both electron-accepting conditions. Isotope analysis was able to provide a first line of evidence for the reaction mechanism of 1,2-DCA biodegradation by the microbial culture. Using a multi-isotope approach incorporating both carbon and hydrogen isotopic data, compound specific isotope analysis also has the potential to determine degradation mechanisms for 1,2-DCA under aerobic conditions where 1,2-DCA is known to be degraded by two distinct enzymatic pathways. Biodegradation of 1

  8. 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.

  9. Quantifying RDX biodegradation in groundwater using δ15N isotope analysis

    NASA Astrophysics Data System (ADS)

    Bernstein, Anat; Adar, Eilon; Ronen, Zeev; Lowag, Harald; Stichler, Willibald; Meckenstock, Rainer U.

    2010-01-01

    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 1.15-1.35 km 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 12.8 years for RDX biodegradation in the upper 15 m of the aquifer, assuming purely aerobic biodegradation, and between 10.9 and 31.2 years, 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 161.5 years, assuming purely aerobic biodegradation, and between 207.5 and 394.3 years, 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.

  10. 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.

  11. 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

  12. 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.

  13. 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.

  14. 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

  15. 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.

  16. 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.

    2014-01-01

    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. Our results obtained from δ13C analysis of amino sugars in selected marine sediment samples showed that muramic acid had isotopic imprints from indigenous bacterial activities, whereas glucosamine and galactosamine were mainly derived from organic detritus. The analysis of stable carbon isotopic compositions of amino sugars opens a promising window for the investigation of microbial metabolisms in marine sediments and the deep marine biosphere.

  17. C & N isotope analysis of diclofenac to distinguish oxidative and reductive transformation and to track commercial products.

    PubMed

    Maier, Michael P; De Corte, Simon; Nitsche, Sebastian; Spaett, Thomas; Boon, Nico; Elsner, Martin

    2014-02-18

    Although diclofenac is frequently found in aquatic systems, its degradability in the environment remains imperfectly understood. On the one hand, evidence from concentration analysis alone is inconclusive if an unknown hydrology impedes a distinction between degradation and dilution. On the other hand, not all transformation products may be detectable. As a new approach, we therefore developed GC-IRMS (gas chromatography-isotope-ratio mass-spectrometry) analysis for carbon and nitrogen isotope measurements of diclofenac. The method uses a derivatization step that can be conducted either online or offline, for optimized throughput or sensitivity, respectively. In combination with on-column injection, the latter method enables determination of diclofenac isotope ratios down to the sub-μgL(-1) range in environmental samples. Degradation in an aerobic sediment-water system showed strong nitrogen isotope fractionation (εN = -7.1‰), whereas reductive diclofenac dechlorination was associated with significant carbon isotope fractionation (εC = -2.0‰). Hence dual element isotope analysis bears potential not only to detect diclofenac degradation, but even to distinguish both transformation pathways in the environment. In an explorative survey, analysis of commercial diclofenac products showed significant differences in carbon and nitrogen isotope ratios, demonstrating a further potential to track, and potentially even to authenticate, commercial production batches. PMID:24397428

  18. 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.

  19. Kinetics of the Reaction of the Heaviest Hydrogen Atom with H2, the 4Heμ + H2 -> 4HeμΗ + H Reaction: Experiments, Accurate Quantal Calculations, and Variational Transition State Theory, including Kinetic Isotope Effects for a Factor of 36.1 in Isotopic Mass

    SciTech Connect

    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 {sup 4}He{mu}, 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 ({mu}SR) measurements of the chemical reaction rate constant of {sup 4}He{mu} with molecular hydrogen, {sup 4}He{mu} + H{sub 2} {yields} {sup 4}He{mu}H + H, at temperatures of 295.5, 405, and 500 K, as well as a {mu}SR measurement of the hyperfine coupling constant of muonic He at high pressures. The experimental rate constants, k{sub He{mu}}, 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{sub He{mu}} 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{sub He{mu}} 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{sub 2} and Mu + H{sub 2} reactions in a novel study of kinetic isotope effects for the H + H{sub 2} reactions over a factor of 36.1 in isotopic mass of the atomic reactant.

  20. Simultaneous stable carbon isotopic analysis of wine glycerol and ethanol by liquid chromatography coupled to isotope ratio mass spectrometry.

    PubMed

    Cabañero, Ana I; Recio, Jose L; Rupérez, Mercedes

    2010-01-27

    A novel procedure was established for the simultaneous characterization of wine glycerol and ethanol (13)C/(12)C isotope ratio, using liquid chromatography/isotope ratio mass spectrometry (LC-IRMS). Several parameters influencing separation of glycerol and ethanol from wine matrix were optimized. Results obtained for 35 Spanish samples exposed no significant differences and very strong correlations (r = 0.99) between the glycerol (13)C/(12)C ratios obtained by an alternative method (gas chromatography/isotope ratio mass spectrometry) and the proposed new methodology, and between the ethanol (13)C/(12)C ratios obtained by the official method (elemental analyzer/isotope ratio mass spectrometry) and the proposed new methodology. The accuracy of the proposed method varied from 0.01 to 0.19 per thousand, and the analytical precision was better than 0.25 per thousand. The new developed LC-IRMS method it is the first isotopic method that allows (13)C/(12)C determination of both analytes in the same run directly from a liquid sample with no previous glycerol or ethanol isolation, overcoming technical difficulties associated with complex sample treatment and improving in terms of simplicity and speed. PMID:20025274

  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. 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.

  3. Isotopically nonstationary 13C flux analysis of Myc-induced metabolic reprogramming in B-cells

    PubMed Central

    Murphy, Taylor A.; Dang, Chi V.; Young, Jamey D.

    2012-01-01

    We assessed several methods of 13C metabolic flux analysis (MFA) and found that isotopically nonstationary MFA achieved maximum flux resolution in cultured P493-6 B-cells, which have been engineered to provide tunable expression of the Myc oncoprotein. Comparison of metabolic flux maps obtained under oncogenic (High) and endogenous (Low) Myc expression levels revealed network-wide reprogramming in response to ectopic Myc expression. High Myc cells relied more heavily on mitochondrial oxidative metabolism than Low Myc cells and globally upregulated their consumption of amino acids relative to glucose. TCA cycle and amphibolic mitochondrial pathways exhibited 2- to 4-fold flux increases in High Myc cells, in contrast to modest increases in glucose uptake and lactate excretion. Because our MFA approach relied exclusively upon isotopic measurements of protein-bound amino acids and RNA-bound ribose, it is readily applicable to more complex tumor models that are not amenable to direct extraction and isotopic analysis of free intracellular metabolites. PMID:22898717

  4. Analysis of the stable carbon isotope composition of formic and acetic acids.

    PubMed

    Lee, Xinqing; Zhang, Like; Huang, Daikuan; An, Ning; Yang, Fang; Jiang, Wei; Fang, Bin

    2013-05-15

    Formic and acetic acids are ubiquitous in the environment and in many biological processes. Analysis of the stable carbon isotope composition (δ(13)C) of formic and acetic acids is important to understanding their biogeochemical cycles. However, it has been faced with poor accuracy and high detection limits due to their low carbon number, high hydrophilicity, and semi-volatility. Here we developed an analytical technique by needle trap and gas chromatography-isotope ratio mass spectrometry (GC-IRMS). The organic acids in aqueous solution were extracted using a NeedlEx needle through purge-and-trap and were analyzed by GC-IRMS for δ(13)C. The procedures incur no isotope fractionation. Defined as the point at which the mean δ(13)C is statistically the same as the given value and the analytical error starts rising, the method's detection limits are 200 and 100 mg/L for formic and acetic acids, respectively, with an uncertainty of approximately 0.5‰ in direct extraction and analysis. They were lowered to 1 mg/L with precision of 0.9‰ after samples were subjected to preconcentration. The method was successfully applied to natural samples as diverse as precipitation, vinegars, ant plasma, and vehicle exhaust, which vary considerably in concentration and matrix of the organic acids. It is applicable to the organic acids in not only aqueous solution but also gaseous phase. PMID:23395975

  5. 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

  6. Absorption spectroscopy of uranium plasma for remote isotope analysis of next-generation nuclear fuel

    NASA Astrophysics Data System (ADS)

    Miyabe, M.; Oba, M.; Iimura, H.; Akaoka, K.; Maruyama, Y.; Ohba, H.; Tampo, M.; Wakaida, I.

    2013-07-01

    To determine experimental conditions suitable for isotope analysis, we studied the plume dynamics of uranium. A uranium oxide sample was ablated by 2nd harmonic radiation from a Nd:YAG laser at a fluence of 0.5 J/cm2. The temporal evolution of the ablation plume was investigated in vacuum and helium environments. In vacuum, the flow velocity perpendicular to the sample surface was determined to be 2.7 km/s for neutral atoms and 4.0 km/s for singly charged atoms. These velocities are about 20 % lower than those of cerium measured under similar conditions. From the evolution of the plume in helium, we found that an observation time of 3-5 μs and an observation height of about 2.5 mm are most suited for obtaining higher sensitivity. Observation times less than 3 μs were unsuitable for precise isotope analysis since the spectral modifications arising from the Doppler splitting effect are different between the two uranium isotopes. Using the established conditions, we evaluated the calibration curve linearity, limit of detection, and precision for three samples having different abundances of 235U.

  7. 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.

  8. 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

  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. 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

  11. 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

  12. Analysis of the hydrogen and oxygen stable isotope ratios of beverage waters without prior water extraction using isotope ratio infrared spectroscopy.

    PubMed

    Chesson, Lesley A; Bowen, Gabriel J; Ehleringer, James R

    2010-11-15

    Hydrogen (δ(2)H) and oxygen (δ(18)O) stable isotope analysis is useful when tracing the origin of water in beverages, but traditional analytical techniques are limited to pure or extracted waters. We measured the isotopic composition of extracted beverage water using both isotope ratio infrared spectroscopy (IRIS; specifically, wavelength-scanned cavity ring-down spectroscopy) and isotope ratio mass spectrometry (IRMS). We also analyzed beer, sodas, juices, and milk 'as is' using IRIS. For IRIS analysis, four sequential injections of each sample were measured and data were corrected for sample-to-sample memory using injections (a) 1-4, (b) 2-4, and (c) 3-4. The variation between δ(2)H and δ(18)O values calculated using the three correction methods was larger for unextracted (i.e., complex) beverages than for waters. The memory correction was smallest when using injections 3-4. Beverage water δ(2)H and δ(18)O values generally fit the Global Meteoric Water Line, with the exception of water from fruit juices. The beverage water stable isotope ratios measured using IRIS agreed well with the IRMS data and fit 1:1 lines, with the exception of sodas and juices (δ(2)H values) and beers (δ(18)O values). The δ(2)H and δ(18)O values of waters extracted from beer, soda, juice, and milk were correlated with complex beverage δ(2)H and δ(18)O values (r = 0.998 and 0.997, respectively) and generally fit 1:1 lines. We conclude that it is possible to analyze complex beverages, without water extraction, using IRIS although caution is needed when analyzing beverages containing sugars, which can clog the syringe and increase memory, or alcohol, a known spectral interference. PMID:20941769

  13. 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.

  14. 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

  15. 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

  16. Improved centroid moment tensor analyses in the NIED AQUA (Accurate and QUick Analysis system for source parameters)

    NASA Astrophysics Data System (ADS)

    Kimura, H.; Asano, Y.; Matsumoto, T.

    2012-12-01

    The rapid determination of hypocentral parameters and their transmission to the public are valuable components of disaster mitigation. We have operated an automatic system for this purpose—termed the Accurate and QUick Analysis system for source parameters (AQUA)—since 2005 (Matsumura et al., 2006). In this system, the initial hypocenter, the moment tensor (MT), and the centroid moment tensor (CMT) solutions are automatically determined and posted on the NIED Hi-net Web site (www.hinet.bosai.go.jp). This paper describes improvements made to the AQUA to overcome limitations that became apparent after the 2011 Tohoku Earthquake (05:46:17, March 11, 2011 in UTC). The improvements included the processing of NIED F-net velocity-type strong motion records, because NIED F-net broadband seismographs are saturated for great earthquakes such as the 2011 Tohoku Earthquake. These velocity-type strong motion seismographs provide unsaturated records not only for the 2011 Tohoku Earthquake, but also for recording stations located close to the epicenters of M>7 earthquakes. We used 0.005-0.020 Hz records for M>7.5 earthquakes, in contrast to the 0.01-0.05 Hz records employed in the original system. The initial hypocenters determined based on arrival times picked by using seismograms recorded by NIED Hi-net stations can have large errors in terms of magnitude and hypocenter location, especially for great earthquakes or earthquakes located far from the onland Hi-net network. The size of the 2011 Tohoku Earthquake was initially underestimated in the AQUA to be around M5 at the initial stage of rupture. Numerous aftershocks occurred at the outer rise east of the Japan trench, where a great earthquake is anticipated to occur. Hence, we modified the system to repeat the MT analyses assuming a larger size, for all earthquakes for which the magnitude was initially underestimated. We also broadened the search range of centroid depth for earthquakes located far from the onland Hi

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

    NASA Astrophysics Data System (ADS)

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

    2013-04-01

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

  18. 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.

  19. 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

  20. 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

  1. Stable isotope ratio analysis to differentiate temporal diets of a free-ranging herbivore.

    PubMed

    Walter, W D; Leslie, D M

    2009-07-01

    Stable isotope ratio analysis (SIRA) of carbon (delta13C) and nitrogen (delta15N) in tissue samples of herbivores can identify photosynthetic pathways (C3 vs. C4) of plants consumed. We present results from free-ranging Rocky Mountain elk (Cervus elaphus) that highlight the ability to differentiate diets using tissue delta13C and delta15N. The signatures of delta13C and delta15N differed in tissues of varying metabolic activity: muscle, a short-term dietary indicator (i.e., 1-2 months) and hoof, a long-term dietary indicator (i.e., 3-12 months). We also documented that delta13C and delta15N values along elk hooves (proximal, middle, distal sections) elucidated temporal shifts in dietary selection. The carbon isotopes of the composite hoof were similar to those of the middle section, but the composite hoof differed in delta(13)C from the distal and proximal sections. The delta13C and delta15N signatures also differed among elk populations, indicating temporal dietary shifts of individuals occupying disparate native range and human-derived agricultural landscapes. Analyses of stable isotopes in various tissues highlighted carbon and nitrogen assimilation through time and differences in the foraging ecology of a rangeland herbivore. PMID:19530151

  2. Isotopic analysis of single uranium and plutonium particles by chemical treatment and mass spectrometry

    NASA Astrophysics Data System (ADS)

    Shinonaga, T.; Esaka, F.; Magara, M.; Klose, D.; Donohue, D.

    2008-11-01

    The isotopic composition of single uranium and plutonium particles was measured with an inductively coupled plasma mass spectrometer (ICP-MS) and a thermal ionization mass spectrometer (TIMS). Particles deposited on a carbon planchet were first analyzed with an energy dispersive X-ray spectrometer (EDX) attached to a scanning electron microscope (SEM) and then transferred on to a silicon wafer using a manipulator. The particle on the silicon wafer was dissolved with nitric acid and the isotopic ratios of U and Pu were measured with ICP-MS and TIMS. The results obtained by both methods for particles of certified reference materials showed good agreement with the certified values within the expected uncertainty. The measurement uncertainties obtained in this study were similar for both mass spectrometric methods. This study was performed to establish the method of particle analysis with SEM, EDX, the particle manipulation and chemical preparation technique, and the measurement of isotopic ratios of U and Pu in a single particle by mass spectrometry.

  3. Compound-Specific Isotope Analysis of Volatile Organosulfur Compounds from Cariaco Basin

    NASA Astrophysics Data System (ADS)

    Raven, M. R.; Sessions, A. L.; Adkins, J. F.; Subhas, A.

    2011-12-01

    Sulfur isotopes have the potential to elucidate important transformations of organic matter in sulfur-rich environments, particularly marine sediments. To date, analytical limitations have restricted such studies either to bulk measurements, which necessarily ignore the diverse constituents of organic matter, or to the analysis of compounds that can be isolated in significant (mg) quantities. By coupling a gas chromatograph to a multicollector ICPMS, we are now able to measure the sulfur isotopic compositions of individual organosulfur compounds in complex environmental samples. Lipids were extracted from a Cariaco Basin sediment core representing approximately 11 kyr of sediment deposition and diagenesis under consistently euxinic conditions. After separation by column chromatography, the nonpolar lipid fractions were found to contain sulfur-bearing species with δ34SCDT values ranging from -11% to +17.5% based on calibration with an internal (SF6) standard. This range of values confirms previous speculation that multiple pathways for organic matter sulfurization must exist in marine sediments, and provides the opportunity to track precursor-product relationships as diagenesis progresses down-core. Repeat measurements consistently demonstrate relative standard deviations for δ34S of between 0.2% and 0.4% for peaks containing only a few pmol S. The relative abundances and isotopic compositions of individual compounds are observed to vary with depth and age. Additional data are being collected and will be presented at the meeting.

  4. Application of nitrogen stable isotope analysis in size-based marine food web and macroecological research.

    PubMed

    Jennings, Simon; Barnes, Carolyn; Sweeting, Christopher J; Polunin, Nicholas V C

    2008-06-01

    Interacting human and environmental pressures influence the structure and dynamics of marine food webs. To describe and predict the effects of these pressures, theoretical advances need to be supported by a capacity to validate the underlying models and assumptions. Here, we review recent applications of nitrogen stable isotope analysis in marine food web and macroecological research, with a focus on work that has paralleled a resurgence of interest in the development and application of size-based models. Nitrogen stable isotope data have been used to estimate intra- and inter-specific variation in trophic level, predator-prey size ratios, transfer efficiency, food chain length, relationships between predator and prey species diversity and the dynamics of energy use. Many of these estimates have contributed to the development, testing and parameterisation of food web and ecosystem models, some of which have been used to establish baselines for assessing the scale of human impacts. The interpretation of results depends on assumed fractionation but, when supported by sensitivity analyses and experimental validation, nitrogen stable isotope data provide valuable insights into the structuring of marine communities and ecosystems. PMID:18438766

  5. Quantitative Metabolome Analysis Based on Chromatographic Peak Reconstruction in Chemical Isotope Labeling Liquid Chromatography Mass Spectrometry.

    PubMed

    Huan, Tao; Li, Liang

    2015-07-21

    Generating precise and accurate quantitative information on metabolomic changes in comparative samples is important for metabolomics research where technical variations in the metabolomic data should be minimized in order to reveal biological changes. We report a method and software program, IsoMS-Quant, for extracting quantitative information from a metabolomic data set generated by chemical isotope labeling (CIL) liquid chromatography mass spectrometry (LC-MS). Unlike previous work of relying on mass spectral peak ratio of the highest intensity peak pair to measure relative quantity difference of a differentially labeled metabolite, this new program reconstructs the chromatographic peaks of the light- and heavy-labeled metabolite pair and then calculates the ratio of their peak areas to represent the relative concentration difference in two comparative samples. Using chromatographic peaks to perform relative quantification is shown to be more precise and accurate. IsoMS-Quant is integrated with IsoMS for picking peak pairs and Zero-fill for retrieving missing peak pairs in the initial peak pairs table generated by IsoMS to form a complete tool for processing CIL LC-MS data. This program can be freely downloaded from the www.MyCompoundID.org web site for noncommercial use. PMID:26086729

  6. 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.

  7. 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

  8. Oxygen isotope analysis of phosphate: improved precision using TC/EA CF-IRMS.

    PubMed

    LaPorte, D F; Holmden, C; Patterson, W P; Prokopiuk, T; Eglington, B M

    2009-06-01

    Oxygen isotope values of biogenic apatite have long demonstrated considerable promise for paleothermometry potential because of the abundance of material in the fossil record and greater resistance of apatite to diagenesis compared to carbonate. Unfortunately, this promise has not been fully realized because of relatively poor precision of isotopic measurements, and exceedingly small size of some substrates for analysis. Building on previous work, we demonstrate that it is possible to improve precision of delta18O(PO4) measurements using a 'reverse-plumbed' thermal conversion elemental analyzer (TC/EA) coupled to a continuous flow isotope ratio mass spectrometer (CF-IRMS) via a helium stream [Correction made here after initial online publication]. This modification to the flow of helium through the TC/EA, and careful location of the packing of glassy carbon fragments relative to the hot spot in the reactor, leads to narrower, more symmetrically distributed CO elution peaks with diminished tailing. In addition, we describe our apatite purification chemistry that uses nitric acid and cation exchange resin. Purification chemistry is optimized for processing small samples, minimizing isotopic fractionation of PO4(-3) and permitting Ca, Sr and Nd to be eluted and purified further for the measurement of delta44Ca and 87Sr/86Sr in modern biogenic apatite and 143Nd/144Nd in fossil apatite. Our methodology yields an external precision of +/- 0.15 per thousand (1sigma) for delta18O(PO4). The uncertainty is related to the preparation of the Ag3PO4 salt, conversion to CO gas in a reversed-plumbed TC/EA, analysis of oxygen isotopes using a CF-IRMS, and uncertainty in constructing calibration lines that convert raw delta18O data to the VSMOW scale. Matrix matching of samples and standards for the purpose of calibration to the VSMOW scale was determined to be unnecessary. Our method requires only slightly modified equipment that is widely available. This fact, and the

  9. Coenzyme F430, quantification and isotope analysis from the Eel River Basin California

    NASA Astrophysics Data System (ADS)

    Bird, L. R.; Fulton, J. M.; Dawson, K.; Orphan, V. J.; Freeman, K. H.

    2012-12-01

    Large amounts of methane are oxidized by communities of methanotrophic archaea and sulphate-reducing bacteria, preventing this greenhouse gas from reaching the atmosphere (Orphan et al., 2001; Scheller et al., 2010). Methyl-coenzyme M reductase, an enzyme traditionally associated with methanogenesis, has recently been linked to the anaerobic oxidation of methane suggesting methane oxidation follows a pathway similar to reverse methanogenesis. Coenzyme F430, a tetrapyrrole-nickel complex within the active site of methyl-coenzyme M, is used in methanogenesis and is hypothesized to play a key role in archaeal methanotrophy (Scheller et al., 2010). We recently developed a method to extract and isolate F430 from natural sediments so it can be purified for carbon and nitrogen stable isotope analysis. Sediments are extracted using an ultrasonic homogenizer, first in water (pH 7), then twice in dilute formic acid (pH 3). The combined extract is neutralized and the F430-containing fraction is isolated using Sephadex and Amberlite column chromatography. Further purification is performed using two dimensional high performance liquid chromatography, first with a reverse phase C-18 column followed by separation on a ThermoFisher Hypercarb column. F430 is then quantified using photo diode array detection with fractions collected for isotope analysis using a nano-scale elemental analyzer isotope ratio mass spectrometer (nano-EA-IRMS; Polissar et al., 2009). Compound identity and purity are confirmed using molar C:N ratios, UV absorbance and MSn detection of the parent ion (m/z 905). Here, we report F430 concentrations and isotopic data determined from active seep sediment cores from the Eel River Basin (California), a site where the anoxic oxidation of methane occurs. A spike in the concentration of F430 is observed at the 3-6 cm depth horizon corresponding with peak abundance in ANME-2/Desulfosarcina/Desulfococcus aggregate counts. Carbon isotope values of F430 are significantly

  10. Source Attribution of Cyanides Using Anionic Impurity Profiling, Stable Isotope Ratios, Trace Elemental Analysis and Chemometrics.

    PubMed

    Mirjankar, Nikhil S; Fraga, Carlos G; Carman, April J; Moran, James J

    2016-02-01

    Chemical attribution signatures (CAS) for chemical threat agents (CTAs), such as cyanides, are being investigated to provide an evidentiary link between CTAs and specific sources to support criminal investigations and prosecutions. Herein, stocks of KCN and NaCN were analyzed for trace anions by high performance ion chromatography (HPIC), carbon stable isotope ratio (δ(13)C) by isotope ratio mass spectrometry (IRMS), and trace elements by inductively coupled plasma optical emission spectroscopy (ICP-OES). The collected analytical data were evaluated using hierarchical cluster analysis (HCA), Fisher-ratio (F-ratio), interval partial least-squares (iPLS), genetic algorithm-based partial least-squares (GAPLS), partial least-squares discriminant analysis (PLSDA), K nearest neighbors (KNN), and support vector machines discriminant analysis (SVMDA). HCA of anion impurity profiles from multiple cyanide stocks from six reported countries of origin resulted in cyanide samples clustering into three groups, independent of the associated alkali metal (K or Na). The three groups were independently corroborated by HCA of cyanide elemental profiles and corresponded to countries each having one known solid cyanide factory: Czech Republic, Germany, and United States. Carbon stable isotope measurements resulted in two clusters: Germany and United States (the single Czech stock grouped with United States stocks). Classification errors for two validation studies using anion impurity profiles collected over five years on different instruments were as low as zero for KNN and SVMDA, demonstrating the excellent reliability associated with using anion impurities for matching a cyanide sample to its factory using our current cyanide stocks. Variable selection methods reduced errors for those classification methods having errors greater than zero; iPLS-forward selection and F-ratio typically provided the lowest errors. Finally, using anion profiles to classify cyanides to a specific stock

  11. Analysis of trace metals (Cu, Cd, Pb, and Fe) in seawater using single batch nitrilotriacetate resin extraction and isotope dilution inductively coupled plasma mass spectrometry.

    PubMed

    Lee, Jong-Mi; Boyle, Edward A; Echegoyen-Sanz, Yolanda; Fitzsimmons, Jessica N; Zhang, Ruifeng; Kayser, Richard A

    2011-02-01

    A simple and accurate low-blank method has been developed for the analysis of total dissolved copper, cadmium, lead, and iron in a small volume (1.3-1.5 mL per element) of seawater. Pre-concentration and salt-separation of a stable isotope spiked sample are achieved by single batch extraction onto nitrilotriacetate (NTA)-type Superflow(®) chelating resin beads (100-2400 beads depending on the element). Metals are released into 0.1-0.5 M HNO(3), and trace metal isotope ratios are determined by ICPMS. The benefit of this method compared to our previous Mg(OH)(2) coprecipitation method is that the final matrix is very dilute so cone-clogging and matrix sensitivity suppression are minimal, while still retaining the high accuracy of the isotope dilution technique. Recovery efficiencies are sensitive to sample pH, number of resin beads added, and the length of time allowed for sample-resin binding and elution; these factors are optimized for each element to yield the highest recovery. The method has a low procedural blank and high sensitivity sufficient for the analysis of pM-nM open-ocean trace metal concentrations. Application of this method to samples from the Bermuda Atlantic Time-Series Study station provides oceanographically consistent Cu, Cd, Pb, and Fe profiles that are in good agreement with other reliable data for this site. In addition, the method can potentially be modified for the simultaneous analysis of multiple elements, which will be beneficial for the analysis of large number of samples. PMID:21237313

  12. Sr and Nd Isotopic and Geochemical Analysis of the Vanda Dike Swarm, Antarctica

    NASA Astrophysics Data System (ADS)

    Bray, B.; Harpp, K. S.; Geist, D.; Garcia, M. O.; Swarr, G. J.; Garman, K. A.; Buck, S. A.; Parcheta, C. E.; Matulaitis, I.

    2009-12-01

    The Vanda dike swarm, in the Dry Valleys of Antarctica, crosscuts synorogenic Cambro-Ordovician granitoid plutons produced during the Ross Orogeny, circa 500 Ma. The emplacement of the dikes broadly coincides with the transition between the cessation of subduction and the onset of extensional magmatism. Recent fieldwork included field documentation of over 600 dikes, with subsequent whole rock major and trace element analysis and Sr and Nd isotopic analyses of a representative subset. Although originally characterized as being compositionally bimodal, the compositions of the dikes range continuously from 48% to 78% SiO2. New radiogenic isotopic data from 24 samples exhibit a surprisingly wide range of ɛNd and 87Sr/86Sri values; the bulk of the samples have an age-corrected ɛNd from -12.7 to -3.0, however a subset of four of the dikes (both mafic and felsic) have ɛNd values ranging from +2.1 to 8.0. The 87Sr/86Sri ratios vary from 0.7085 to 0.7118. Notably, there is significant overlap between the isotopic signatures of the mafic and felsic rocks and no strong correlation between ɛNd and 87Sr/86Sri. Likewise, there is no correlation between either isotopic ratio and SiO2. These variations indicate that the Vanda dikes may be derived from compositionally heterogeneous sources. Additionally, Nd model ages (τDM) of the felsic dikes yield an average of ~900 Ma, suggesting derivation from a Neoproterozoic crustal source. The Vanda dike samples’ 87Sr/86Sri overlap with the high end of the range defined by the youngest plutons in the region emplaced during the Ross Orogeny (adakitic DV1b, monzonitic DV2; Cox et al., 2000). Similarly, ɛNd values of the Vanda samples most closely resemble those of the DV1b and DV2 plutons, but also extend to significantly more negative and more positive values. None of the isotopic signatures of the dikes are similar to those of the older, orogenic granites in the region (DV1a), which have lower 87Sr/86Sri averages than both the

  13. TPASS: a gamma-ray spectrum analysis and isotope identification computer code

    SciTech Connect

    Dickens, J.K.

    1981-03-01

    The gamma-ray spectral data-reduction and analysis computer code TPASS is described. This computer code is used to analyze complex Ge(Li) gamma-ray spectra to obtain peak areas corrected for detector efficiencies, from which are determined gamma-ray yields. These yields are compared with an isotope gamma-ray data file to determine the contributions to the observed spectrum from decay of specific radionuclides. A complete FORTRAN listing of the code and a complex test case are given.

  14. 2H Stable Isotope Analysis of Tooth Enamel: A Pilot Study

    NASA Astrophysics Data System (ADS)

    Holobinko, Anastasia; Kemp, Helen; Meier-Augenstein, Wolfram; Prowse, Tracy; Ford, Susan

    2010-05-01

    Stable isotope analysis of biogenic tissues such as tooth enamel and bone mineral has become a well recognized and increasingly important method for determining provenance of human remains, and has been used successfully in bioarchaeological studies as well as forensic investigations (Lee-Thorp, 2008; Meier-Augenstein and Fraser, 2008). Particularly, 18O and 2H stable isotopes are well established proxies as environmental indicators of climate (temperature) and source water and are therefore considered as indicators of geographic life trajectories of animals and humans (Hobson et al., 2004; Schwarcz and Walker, 2006). While methodology for 2H analysis of human hair, fingernails, and bone collagen is currently used to determine geographic origin and identify possible migration patterns, studies involving the analysis of 2H in tooth enamel appear to be nonexistent in the scientific literature. The apparent lack of research in this area is believed to have two main reasons. (1) Compared to the mineral calcium hydroxylapatite Ca10(PO4)6(OH)2, in tooth enamel forming bio-apatite carbonate ions replace some of the hydroxyl ions at a rate of one CO32 replacing two OH, yet published figures for the degree of substitution vary (Wopenka and Pasteris, 2005). (2) Most probably due to the aforementioned no published protocols exist for sample preparation and analytical method to obtain δ2H-values from the hydroxyl fraction of tooth enamel. This dilemma has been addressed through a pilot study to establish feasibility of 2H stable isotope analysis of ground tooth enamel by continuous-flow isotope ratio mass spectrometry (IRMS) coupled on-line to a high-temperature conversion elemental analyzer (TC/EA). An array of archaeological and modern teeth has been analyzed under different experimental conditions, and results from this pilot study are being presented. References: Lee-Thorp, J.A. (2008) Archaeometry, 50, 925-950 Meier-Augenstein, W. and Fraser, I. (2008) Science & Justice

  15. OpenMebius: An Open Source Software for Isotopically Nonstationary 13C-Based Metabolic Flux Analysis

    PubMed Central

    Furusawa, Chikara

    2014-01-01

    The in vivo measurement of metabolic flux by 13C-based metabolic flux analysis (13C-MFA) provides valuable information regarding cell physiology. Bioinformatics tools have been developed to estimate metabolic flux distributions from the results of tracer isotopic labeling experiments using a 13C-labeled carbon source. Metabolic flux is determined by nonlinear fitting of a metabolic model to the isotopic labeling enrichment of intracellular metabolites measured by mass spectrometry. Whereas 13C-MFA is conventionally performed under isotopically constant conditions, isotopically nonstationary 13C metabolic flux analysis (INST-13C-MFA) has recently been developed for flux analysis of cells with photosynthetic activity and cells at a quasi-steady metabolic state (e.g., primary cells or microorganisms under stationary phase). Here, the development of a novel open source software for INST-13C-MFA on the Windows platform is reported. OpenMebius (Open source software for Metabolic flux analysis) provides the function of autogenerating metabolic models for simulating isotopic labeling enrichment from a user-defined configuration worksheet. Analysis using simulated data demonstrated the applicability of OpenMebius for INST-13C-MFA. Confidence intervals determined by INST-13C-MFA were less than those determined by conventional methods, indicating the potential of INST-13C-MFA for precise metabolic flux analysis. OpenMebius is the open source software for the general application of INST-13C-MFA. PMID:25006579

  16. Stable isotope analysis of energy dynamics in aquatic ecosystems suggests trophic shifts following severe wildfire

    NASA Astrophysics Data System (ADS)

    Martens, A. M.; Silins, U.; Bladon, K. D.; Williams, C.; Wagner, M. J.; Luchkow, E.

    2015-12-01

    Wildfire alters landscapes and can have significant impacts on stream ecosystems. The 2003 Lost Creek wildfire was one of the most severe on Alberta's eastern rocky mountain slopes, resulting in elevated sediment production and nutrient (phosphorus, nitrogen, and carbon) export in impacted streams. These resulted in increased algal productivity and macroinvertebrate abundance and diversity, and as a result, fish in watersheds draining wildfire affected catchments were larger than those in the same age class from reference (unburned) watersheds. In the present investigation, stable isotope analysis of C and N was utilized to evaluate ecosystem energy dynamics and describe trophic relationships in those watersheds. Aquatic invertebrates from burned catchments showed enrichment in δ13C and δ15N relative to algae suggesting a reliance on algae (autochthony) as a primary source of energy. Invertebrates from unburned systems were depleted in δ13C relative to algae indicating reliance on allochthonous or terrestrial primary energy sources. Preliminary analysis of δ15N in macroinvertebrates showed slight enrichment in burned catchments suggesting a trophic shift. More comprehensive macroinvertebrate sampling and identification has been conducted; isotopic analysis will provide greater resolution of how specific families within feeding guilds have been affected by wildfire. This will provide more robust insights into how wildfires may impact stream ecology in mountain environments.

  17. Origin assessment of green coffee (Coffea arabica) by multi-element stable isotope analysis of caffeine.

    PubMed

    Weckerle, Bernhard; Richling, Elke; Heinrich, Sandra; Schreier, Peter

    2002-11-01

    The delta(13)C(VPDB), delta(2)H(VSMOW) and delta(18)O(VSMOW) values of caffeine isolated from Arabica green coffee beans of different geographical origin have been determined by isotope ratio mass spectrometry (IRMS) using elemental analysis (EA) in the "combustion" (C) and "pyrolysis" (P) modes (EA-C/P-IRMS). In total, 45 coffee samples (20 from Central and South America, 16 from Africa, six from Indonesia, and three from Jamaica and Hawaii) were analysed, as well as three reference samples of synthetic caffeine. Validation was performed by excluding isotope discrimination in the course of sample preparation and determining linear dynamic ranges for EA-P-IRMS measurements. The values for caffeine from green coffee ranged from -25.1 to - 29.9 per thousand, -109 to -198 per thousand, and +2.0 to -12.0 per thousand for delta(13)C(VPDB), delta(2)H(VSMOW), and delta(18)O(VSMOW), respectively. Data evaluation by linear discrimination analysis (LDA) and by classification and regression tree (CART) analysis revealed the delta(18)O(VSMOW) values to be highly significant. Use of LDA on the delta(2)H(VSMOW) and delta(18)O(VSMOW) data from coffee of African and Central/South American provenance led to error rates of 5.7% and 7.7% for adaption and cross validation, respectively. PMID:12434246

  18. Partial Safety Analysis for a Reduced Enrichment Core for the High Flux Isotope Reactor

    SciTech Connect

    Primm, Trent

    2008-01-01

    A computational model of the reactor core of the High Flux Isotope Rector (HFIR) was developed in order to analyze non-destructive accidents caused by transients during reactor operation. Such a model was built based on the available description parameters as provided by the latest version of the nuclear analysis software package called Program for the Analysis of Reactor Transients (PARET). Analysis performed with the model constructed was compared with previous data obtained with other tools in order to benchmark the code. Finally, the model was used to analyze the behavior of the reactor under transients using a different nuclear fuel with lower enrichment of uranium (LEU) than the fuel currently used, which has a high enrichment of uranium (HEU). The study shows that the presence of fertile isotopes in LEU fuel which increases the neutron resonance absorption reduces the impact of transients on the fuel and enhances the negative reactivity feedback, thus making LEU fuel a safe alternative fuel for the reactor core.

  19. Fingerprinting TCE in a bedrock aquifer using compound-specific isotope analysis.

    PubMed

    Lojkasek-Lima, Paulo; Aravena, Ramon; Parker, Beth L; Cherry, John A

    2012-01-01

    A dual isotope approach based on compound-specific isotope analysis (CSIA) of carbon (C) and chlorine (Cl) was used to identify sources of persistent trichloroethylene (TCE) that caused the shut-down in 1994 of a municipal well in an extensive fractured dolostone aquifer beneath Guelph, Ontario. Several nearby industrial properties have known subsurface TCE contamination; however, only one has created a comprehensive monitoring network in the bedrock. The impacted municipal well and many monitoring wells were sampled for volatile organic compounds (VOCs), inorganic parameters, and CSIA. A wide range in isotope values was observed at the study site. The TCE varies between -35.6‰ and -21.8‰ and from 1.6‰ to 3.2‰ for δ(13) C and δ(37) Cl, respectively. In case of cis-1,2-dichloroethene, the isotope values range between -36.3‰ and -18.9‰ and from 2.4‰ to 4.7‰ for δ(13) C and δ(37) Cl, respectively. The dual isotope approach represented by a plot of δ(13) C vs. δ(37) Cl shows the municipal well samples grouped in a domain clearly separate from all other samples from the property with the comprehensive well network. The CSIA results collected under non-pumping and short-term pumping conditions thus indicate that this particular property, which has been studied intensively for several years, is not a substantial contributor of the TCE presently in the municipal well under non-pumping conditions. This case study demonstrates that CSIA signatures would have been useful much earlier in the quest to examine sources of the TCE in the municipal well if bedrock monitoring wells had been located at several depths beneath each of the potential TCE-contributing properties. Moreover, the CSIA results show that microbial reductive dechlorination of TCE occurs in some parts of the bedrock aquifer. At this site, the use of CSIA for C and Cl in combination with analyses of VOC and redox parameters proved to be important due to the complexity introduced by

  20. In-situ Strontium Isotopes Analysis on Single Conodont Apatite by LA-MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    Zhao, L.; Zhang, L.; Chen, Z. Q.; Ma, D.; Qiu, H.; Lv, Z.; Hu, Z.; Wang, F.

    2014-12-01

    Strontium isotope played an important role in stratigraphic chronology and sedimentary geochemistry research (McArthur et al., 2001). Conodonts is a kind of extinct species of marine animals and widely distributed in marine sediments all over the world. Rich in radiogenic Sr contents and difficulty to be affected during diagenesis alteration makes conodonts a good choice in seawater Sr isotope composition studies (John et al., 2008). Conodont samples were collected from 24th to 39th layer across Permian-Triassic boundary at Meishan D section (GSSP), Zhejiang Province, South China (Yin et al., 2001). Conodonts was originated from fresh limestone and only conodont elements with CAI<2 were chosen for in-situ strontium isotope analysis using laser-ablation multi-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS). Conodont samples are from totally 25 layers in seven conodont zones making it possible for a high resolution 87Sr/ 86Sr curve reconstruction during the Permian-Triassic transition. 87Sr/ 86Sr ratio kept a relatively high value (0.70752) in the middle part of the Clarkina yini zone and a lower value (0.70634) in the upperpart of Clarkina taylorae zone. Of which, 87Sr/ 86Sr ratio emerged a rapid decrease within the Clarkina taylorae zone. After a subsequent increase, 87Sr/ 86Sr ratio dropped to 0.70777 in the Isarcicella staeschei zone. These results helps providing reference data for the biological mass extinction events during the Permian-Triassic transition. Our study also makes is possible for high resolution 87Sr/ 86Sr ratio testing on the single conodont apatite and riched the in-situ studies on the conodont apatite, which of great significance for the future conodont Sr isotope research (Zhao et al., 2009; Zhao et al., 2013). Keywords: Conodonts, Strontium isotope, LA-MC-ICP-MS, Permian-Triassic transition, Meishan D section [1] John et al., 2008 3P[2] McArthur et al., 2001 J. of Geology [3] Yin et al., 2001 Episodes [4] Zhao et al

  1. Evaluation of Stable Isotope Analysis as a Tool to Determine Nitrate Sources in Irish Groundwaters

    NASA Astrophysics Data System (ADS)

    Minet, E.; Coxon, C.; Kalin, R.

    2004-12-01

    & Technology, 35, 1840-1844. Silva, S.R.; Kendall, C.; Wilkison, D.H.; Ziegler, A.C.; Chang, C.C.Y.; Avanzino, R.J. (2000) A new method for collection of nitrate from fresh water and the analysis of nitrogen and oxygen isotope ratios. Journal of Hydrology, 228, 22-36.

  2. Spatially Resolved, In Situ Carbon Isotope Analysis of Archean Organic Matter

    NASA Technical Reports Server (NTRS)

    Williford, Kenneth H.; Ushikubo, Takayuki; Lepot, Kevin; Hallmann, Christian; Spicuzza, Michael J.; Eigenbrode, Jennifer L.; Summons, Roger E.; Valley, John W.

    2011-01-01

    Spatiotemporal variability in the carbon isotope composition of sedimentary organic matter (OM) preserves information about the evolution of the biosphere and of the exogenic carbon cycle as a whole. Primary compositions, and imprints of the post-depositional processes that obscure them, exist at the scale of individual sedimentary grains (mm to micron). Secondary ion mass spectrometry (SIMS) (1) enables analysis at these scales and in petrographic context, (2) permits morphological and compositional characterization of the analyte and associated minerals prior to isotopic analysis, and (3) reveals patterns of variability homogenized by bulk techniques. Here we present new methods for in situ organic carbon isotope analysis with sub-permil precision and spatial resolution to 1 micron using SIMS, as well as new data acquired from a suite of Archean rocks. Three analytical protocols were developed for the CAMECA ims1280 at WiscSIMS to analyze domains of varying size and carbon concentration. Average reproducibility (at 2SD) using a 6 micron spot size with two Faraday cup detectors was 0.4 %, and 0.8 % for analyses using 1 micron and 3 micron spot sizes with a Faraday cup (for C-12) and an electron multiplier (for C-13). Eight coals, two ambers, a shungite, and a graphite were evaluated for micron-scale isotopic heterogeneity, and LCNN anthracite (delta C-13 = -23.56 +/- 0.1 %, 2SD) was chosen as the working standard. Correlation between instrumental bias and H/C was observed and calibrated for each analytical session using organic materials with H/C between 0.1 and 1.5 (atomic), allowing a correction based upon a C-13H/C-13 measurement included in every analysis. Matrix effects of variable C/SiO2 were evaluated by measuring mm to sub-micron graphite domains in quartzite from Bogala mine, Sri Lanka. Apparent instrumental bias and C-12 count rate are correlated in this case, but this may be related to a crystal orientation effect in graphite. Analyses of amorphous

  3. Stable Nitrogen and Oxygen Isotope Analysis of Nitrate using Denitrifying Bacteria

    NASA Astrophysics Data System (ADS)

    Edenburn, L.; Michalski, G. M.

    2009-12-01

    The total isotopic composition of nitrate is used for identifying the origin and fate of nitrate in atmospheric, terrestrial and aquatic systems. The analysis of δ 18O, δ15N, and Δ17O values each give important and unique information about the sources and sinks of nitrate in these systems. Currently, there is no published method that allows for the simultaneous determination of δ18O, δ15N, and Δ17O of nitrate. Cascotti designed a novel method for measurement of δ18O and δ15N in nitrate but not Δ17O. This denitrifier method is based on the isotope ratio analysis of nitrous oxide generated by reduction of nitrate by cultured denitrifying bacteria. Kaiser then altered Cascotti's denitrifier method by converting N2O into O2 followed by the quantitative measurement δ18O and Δ17O, however δ15N was not measured. Here we present preliminary data on δ15N, δ18O, Δ17O values of N2 and O2 generated by the disproportionation of bacterial produced N2O. During the process of denitrification, nitrates are converted to nitrogen gas via a series of intermediate gaseous nitrogen oxide products. This is possible due to the presence of heterotrophic bacteria or autotrophic denitrifiers in select bacteria. Thus, we have chosen three distinct bacteria for the investigation of nitrate reduction for this study: Pseudomonas aureofaciens, Bacillus halodenitrificans, and Achromobacter cycloclastes. They each contain the copper-containing nitrite reductase necessary for the catalyzation of nitrate in order to complete the nitrogen cycle by returning N2 to the atmosphere. Bacillus halodenitrificans has the advantage of being an anaerobic halotolerant (salt-tolerant) denitrifier. Many of our samples have a high saline content; also, pre-concentration techniques using anion resin require elution using high ionic strength solutions. Further, high saline growth solutions limit contamination from other bacteria or organisms. Our efforts also focus on the conversion of N2O over a gold

  4. Tracing carbon flow in an arctic marine food web using fatty acid-stable isotope analysis.

    PubMed

    Budge, S M; Wooller, M J; Springer, A M; Iverson, S J; McRoy, C P; Divoky, G J

    2008-08-01

    Global warming and the loss of sea ice threaten to alter patterns of productivity in arctic marine ecosystems because of a likely decline in primary productivity by sea ice algae. Estimates of the contribution of ice algae to total primary production range widely, from just 3 to >50%, and the importance of ice algae to higher trophic levels remains unknown. To help answer this question, we investigated a novel approach to food web studies by combining the two established methods of stable isotope analysis and fatty acid (FA) analysis--we determined the C isotopic composition of individual diatom FA and traced these biomarkers in consumers. Samples were collected near Barrow, Alaska and included ice algae, pelagic phytoplankton, zooplankton, fish, seabirds, pinnipeds and cetaceans. Ice algae and pelagic phytoplankton had distinctive overall FA signatures and clear differences in delta(13)C for two specific diatom FA biomarkers: 16:4n-1 (-24.0+/-2.4 and -30.7+/-0.8 per thousand, respectively) and 20:5n-3 (-18.3+/-2.0 and -26.9+/-0.7 per thousand, respectively). Nearly all delta(13)C values of these two FA in consumers fell between the two stable isotopic end members. A mass balance equation indicated that FA material derived from ice algae, compared to pelagic diatoms, averaged 71% (44-107%) in consumers based on delta(13)C values of 16:4n-1, but only 24% (0-61%) based on 20:5n-3. Our estimates derived from 16:4n-1, which is produced only by diatoms, probably best represented the contribution of ice algae relative to pelagic diatoms. However, many types of algae produce 20:5n-3, so the lower value derived from it likely represented a more realistic estimate of the proportion of ice algae material relative to all other types of phytoplankton. These preliminary results demonstrate the potential value of compound-specific isotope analysis of marine lipids to trace C flow through marine food webs and provide a foundation for future work. PMID:18481094

  5. Identification of Methanotrophic Lipid Biomarkers in Cold-Seep Mussel Gills: Chemical and Isotopic Analysis

    NASA Technical Reports Server (NTRS)

    Jahnke, Linda L.; Summons, Roger E.; Dowling, Lesley M.; Zahiralis, Karen D.

    1995-01-01

    A lipid analysis of the tissues of a cold-seep mytilid mussel collected from the Louisiana slope of the Gulf of Mexico was used in conjunction with a compound-specific isotope analysis to demonstrate the presence of methanotrophic symbionts in the mussel gill tissue and to demonstrate the host's dependence on bacterially synthesized metabolic intermediates. The gill tissue contained large amounts of group-specific methanotrophic biomarkers, bacteriohopanoids, 4-methylsterols, lipopolysaccharide-associated hydroxy fatty acids, and type I-specific 16:1 fatty acid isomers with bond positions at delta-8, delta-10, and delta-ll. Only small amounts of these compounds were detected in the mantle or other tissues of the host animal. A variety of cholesterol and 4-methylsterol isomers were identified as both free and steryl esters, and the sterol double bond positions suggested that the major bacterially derived gill sterol(11.0% 4(alpha)-methyl-cholesta-8(14), 24-dien-3(beta)-ol) was converted to host cholesterol (64.2% of the gill sterol was cholest-5-en-3(beta)-ol). The stable carbon isotope values for gill and mantle preparations were, respectively, -59.0 and -60.4 per thousand for total tissue, -60.6 and -62.4 per thousand for total lipids, -60.2 and -63.9 per thousand for phospholipid fatty acids, and -71.8 and -73.8 per thousand for sterols. These stable carbon isotope values revealed that the relative fractionation pattern was similar to the patterns obtained in pure culture experiments with methanotrophic bacteria further supporting the conversion of the bacterial methyl-sterol pool.

  6. Application Of Stable Isotope Analysis To Study Temporal Changes In Foraging Ecology In A Highly Endangered Amphibian

    PubMed Central

    Gillespie, J. Hayley

    2013-01-01

    Background Understanding dietary trends for endangered species may be essential to assessing the effects of ecological disturbances such as habitat modification, species introductions or global climate change. Documenting temporal variation in prey selection may also be crucial for understanding population dynamics. However, the rarity, secretive behaviours and obscure microhabitats of some endangered species can make direct foraging observations difficult or impossible. Furthermore, the lethality or invasiveness of some traditional methods of dietary analysis (e.g. gut contents analysis, gastric lavage) makes them inappropriate for such species. Stable isotope analysis facilitates non-lethal, indirect analysis of animal diet that has unrealized potential in the conservation of endangered organisms, particularly amphibians. Methodology/findings I determined proportional contributions of aquatic macroinvertebrate prey to the diet of an endangered aquatic salamander Eurycea sosorum over a two-year period using stable isotope analysis of 13/12C and 15/14N and the Bayesian stable isotope mixing model SIAR. I calculated Strauss’ dietary electivity indices by comparing these proportions with changing relative abundance of potential prey species through time. Stable isotope analyses revealed that a previously unknown prey item (soft-bodied planarian flatworms in the genus Dugesia) made up the majority of E. sosorum diet. Results also demonstrate that E. sosorum is an opportunistic forager capable of diet switching to include a greater proportion of alternative prey when Dugesia populations decline. There is also evidence of intra-population dietary variation. Conclusions/significance Effective application of stable isotope analysis can help circumvent two key limitations commonly experienced by researchers of endangered species: the inability to directly observe these species in nature and the invasiveness or lethality of traditional methods of dietary analysis. This

  7. Proteome Scale-Protein Turnover Analysis Using High Resolution Mass Spectrometric Data from Stable-Isotope Labeled Plants.

    PubMed

    Fan, Kai-Ting; Rendahl, Aaron K; Chen, Wen-Ping; Freund, Dana M; Gray, William M; Cohen, Jerry D; Hegeman, Adrian D

    2016-03-01

    Protein turnover is an important aspect of the regulation of cellular processes for organisms when responding to developmental or environmental cues. The measurement of protein turnover in plants, in contrast to that of rapidly growing unicellular organismal cultures, is made more complicated by the high degree of amino acid recycling, resulting in significant transient isotope incorporation distributions that must be dealt with computationally for high throughput analysis to be practical. An algorithm in R, ProteinTurnover, was developed to calculate protein turnover with transient stable isotope incorporation distributions in a high throughput automated manner using high resolution MS and MS/MS proteomic analysis of stable isotopically labeled plant material. ProteinTurnover extracts isotopic distribution information from raw MS data for peptides identified by MS/MS from data sets of either isotopic label dilution or incorporation experiments. Variable isotopic incorporation distributions were modeled using binomial and beta-binomial distributions to deconvolute the natural abundance, newly synthesized/partial-labeled, and fully labeled peptide distributions. Maximum likelihood estimation was performed to calculate the distribution abundance proportion of old and newly synthesized peptides. The half-life or turnover rate of each peptide was calculated from changes in the distribution abundance proportions using nonlinear regression. We applied ProteinTurnover to obtain half-lives of proteins from enriched soluble and membrane fractions from Arabidopsis roots. PMID:26824330

  8. A new method for stable carbon isotope analysis of chlorofluorocarbons in contaminated groundwater

    NASA Astrophysics Data System (ADS)

    Horst, Axel; Lacrampe-Couloume, Georges; Sherwood Lollar, Barbara

    2015-04-01

    Chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) have been widely used as refrigerants, propellants, solvents, foaming agents and are important intermediates in the production of anesthetics and other fluorinated compounds. Due to their ozone depletion potential, production was banned for most uses under the Montreal Protocol (1987) and its amendments and atmospheric mixing ratios have started to decrease. In addition to the atmosphere, CFCs and HCFCs have been detected in groundwater, and emissions from various sources such as landfill sites are still ongoing. Previous studies have shown that both abiotic and biotic transformation of CFCs may occur under certain conditions. To investigate degradation that may take place in soils and groundwaters, a purge and trap method (P&T) has been developed to measure the stable carbon isotopic composition of CFCs and HCFCs extracted from waters. A set of pure phase working standards (HCFC-22, CFC-11, CFC-113) has been prepared offline and characterized by sealed tube combustion dual inlet mass spectrometry. Comparison between isotopic standards and CFCs extracted by our method demonstrates the sample P&T extraction steps do not induce significant δ13C fractionation (lt;0.5 per mill). Standards characterized by continuous flow CSIA (compound specific isotope analysis) after extraction agree with offline characterized values. Evaporation experiments were carried out to investigate any isotope effects due to volatile loss that might occur either due to sampling methods or sample handling in the lab. Monitoring δ13C values during progressive evaporation showed small isotopic fractionation associated with evaporation. Enrichment factors, obtained from Rayleigh plots, showed inverse isotope fractionation i.e depletion in 13C in the remaining compound. Notably, this effect is in the opposite direction to the fractionation (13C enrichment) that is likely to be associated with abiotic or biotic transformation effects

  9. Development of Analytical Protocols For Organics and Isotopes Analysis on the 2009 MARS Science Laboratory.

    NASA Technical Reports Server (NTRS)

    Mahaffy, P. R.

    2006-01-01

    The Mars Science Laboratory, under development for launch in 2009, is designed explore and quantitatively asses a local region on Mars as a potential habitat for present or past life. Its ambitious goals are to (1) assess the past or present biological potential of the target environment, (2) to characterize the geology and geochemistry at the MSL landing site, and (3) to investigate planetary processes that influence habitability. The planned capabilities of the rover payload will enable a comprehensive search for organic molecules, a determination of definitive mineralogy of sampled rocks and fines, chemical and isotopic analysis of both atmospheric and solid samples, and precision isotope measurements of several volatile elements. A range of contact and remote surface and subsurface survey tools will establish context for these measurements and will facilitate sample identification and selection. The Sample Analysis at Mars (SAM) suite of MSL addresses several of the mission's core measurement goals. It includes a gas chromatograph, a mass spectrometer, and a tunable laser spectrometer. These instruments will be designed to analyze either atmospheric samples or gases extracted from solid phase samples such as rocks and fines. We will describe the range of measurement protocols under development and study by the SAM engineering and science teams for use on the surface of Mars.

  10. Biotransformation of benzotriazoles: insights from transformation product identification and compound-specific isotope analysis.

    PubMed

    Huntscha, Sebastian; Hofstetter, Thomas B; Schymanski, Emma L; Spahr, Stephanie; Hollender, Juliane

    2014-04-15

    Benzotriazoles are widely used domestic and industrial corrosion inhibitors and have become omnipresent organic micropollutants in the aquatic environment. Here, the range of aerobic biological degradation mechanisms of benzotriazoles in activated sludge was investigated. Degradation pathways were elucidated by identifying transient and persistent transformation products in batch experiments using liquid chromatography-high-resolution tandem mass spectrometry (LC-HR-MS/MS). In addition, initial reactions were studied using compound-specific isotope analysis (CSIA). Biodegradation half-lives of 1.0 days for 1H-benzotriazole, 8.5 days for 4-methyl-1H-benzotriazole, and 0.9 days for 5-methyl-1H-benzotriazole with activated sludge confirmed their known partial persistence in conventional wastewater treatment. Major transformation products were identified as 4- and 5-hydroxy-1H-benzotriazole for the degradation of 1H-benzotriazole, and 1H-benzotriazole-5-carboxylic acid for the degradation of 5-methyl-1H-benzotriazole. These transformation products were found in wastewater effluents, showing their environmental relevance. Many other candidate transformation products, tentatively identified by interpretation of HR-MS/MS spectra, showed the broad range of possible reaction pathways including oxidation, alkylation, hydroxylation and indicate the significance of cometabolic processes for micropollutant degradation in biological wastewater treatment in general. The combination of evidence from product analysis with the significant carbon and nitrogen isotope fractionation suggests that aromatic monohydroxylation is the predominant step during the biotransformation of 1H-benzotriazole. PMID:24621328

  11. Partial Safety Analysis for a Reduced Uranium Enrichment Core for the High Flux Isotope Reactor

    SciTech Connect

    Primm, Trent; Gehin, Jess C

    2009-04-01

    A computational model of the reactor core of the High Flux Isotope Rector (HFIR) was developed in order to analyze non-destructive accidents caused by transients during reactor operation. The reactor model was built for the latest version of the nuclear analysis software package called Program for the Analysis of Reactor Transients (PARET). Analyses performed with the model constructed were compared with previous data obtained with other tools in order to benchmark the code. Finally, the model was used to analyze the behavior of the reactor under transients using a different nuclear fuel with lower enrichment of uranium (LEU) than the fuel currently used, which has a high enrichment of uranium (HEU). The study shows that the presence of fertile isotopes in LEU fuel, which increases the neutron resonance absorption, reduces the impact of transients on the fuel and enhances the negative reactivity feedback, thus, within the limitations of this study, making LEU fuel appear to be a safe alternative fuel for the reactor core.

  12. Regional movement patterns of a small-bodied shark revealed by stable-isotope analysis.

    PubMed

    Munroe, S E M; Heupel, M R; Fisk, A T; Logan, M; Simpfendorfer, C A

    2015-05-01

    This study used stable-isotope analysis to define the nearshore regional residency and movements of the small-bodied Australian sharpnose shark Rhizoprionodon taylori. Plasma and muscle δ(13) C and δ(15) N of R. taylori were collected from across five embayments and compared with values of seagrass and plankton from each bay. Linear distances between adjacent bays ranged from 30 to 150 km. There was a positive geographic correlation between R. taylori tissue and environmental δ(13) C values. Populations with the highest tissue δ(15) N were collected from bays that had the highest environmental δ(15) N values. These results suggest that R. taylori did not forage more than 100 km away from their capture location within 6 months to 1 year. The successful application of isotope analysis to define R. taylori movement demonstrates that this technique may be used in addition to traditional methods to study the movement of sharks, even within similar habitats across regionally small spatial scales (<100 km). PMID:25846994

  13. Trophic position of soil nematodes in boreal forests as indicated by stable isotope analysis

    NASA Astrophysics Data System (ADS)

    Kudrin, Alexey; Tsurikov, Sergey

    2016-04-01

    Despite the well-developed trophic classification of soil nematodes, their position in soil food webs is still little understood. Observed deviations from the typical feeding strategy indicate that a simplified trophic classification probably does not fully reflect actual trophic interactions. Furthermore, the extent and functional significance of nematodes as prey for other soil animals remains unknown. Stable isotope analysis (SIA) is powerful tool for investigating the structure of soil food webs, but its application to the study of soil nematodes has been limited to only a few studies. We used stable isotope analysis to gain a better understanding of trophic links of several groups of soil nematodes in two boreal forests on albeluvisol. We investigated four taxonomic groups of nematodes: Mononchida, Dorylaimida, Plectidae and Tylenchidae (mostly from the genus Filenchus), that according to the conventional trophic classification represent predators, omnivores, bacterivores and root-fungal feeders, respectively. To assess the trophic position of nematodes, we used a comparison against a set of reference species including herbivorous, saprophagous and predatory macro-invertebrates, oribatid and mesostigmatid mites, and collembolans. Our results suggest that trophic position of the investigated groups of soil nematodes generally corresponds to the conventional classification. All nematodes were enriched in 13C relative to Picea abies roots and litter, and mycorrhizal fungal mycelium. Root-fungal feeders Tylenchidae had δ15N values similar to those of earthworms, enchytraeids and Entomobrya collembolans, but slightly lower δ13C values. Bacterivorous Plectidae were either equal or enriched in 15N compared with saprophagous macroinvertebrates and most mesofauna species. Omnivorous Dorylaimida and predatory Mononchida were further enriched in 15N and their isotopic signature was similar to that of predatory arthropods. These data confirm a clear separation of

  14. Slight pressure imbalances can affect accuracy and precision of dual inlet-based clumped isotope analysis.

    PubMed

    Fiebig, Jens; Hofmann, Sven; Löffler, Niklas; Lüdecke, Tina; Methner, Katharina; Wacker, Ulrike

    2016-01-01

    It is well known that a subtle nonlinearity can occur during clumped isotope analysis of CO2 that - if remaining unaddressed - limits accuracy. The nonlinearity is induced by a negative background on the m/z 47 ion Faraday cup, whose magnitude is correlated with the intensity of the m/z 44 ion beam. The origin of the negative background remains unclear, but is possibly due to secondary electrons. Usually, CO2 gases of distinct bulk isotopic compositions are equilibrated at 1000 °C and measured along with the samples in order to be able to correct for this effect. Alternatively, measured m/z 47 beam intensities can be corrected for the contribution of secondary electrons after monitoring how the negative background on m/z 47 evolves with the intensity of the m/z 44 ion beam. The latter correction procedure seems to work well if the m/z 44 cup exhibits a wider slit width than the m/z 47 cup. Here we show that the negative m/z 47 background affects precision of dual inlet-based clumped isotope measurements of CO2 unless raw m/z 47 intensities are directly corrected for the contribution of secondary electrons. Moreover, inaccurate results can be obtained even if the heated gas approach is used to correct for the observed nonlinearity. The impact of the negative background on accuracy and precision arises from small imbalances in m/z 44 ion beam intensities between reference and sample CO2 measurements. It becomes the more significant the larger the relative contribution of secondary electrons to the m/z 47 signal is and the higher the flux rate of CO2 into the ion source is set. These problems can be overcome by correcting the measured m/z 47 ion beam intensities of sample and reference gas for the contributions deriving from secondary electrons after scaling these contributions to the intensities of the corresponding m/z 49 ion beams. Accuracy and precision of this correction are demonstrated by clumped isotope analysis of three internal carbonate standards. The

  15. Re-evaluation of interferences of doubly charged ions of heavy rare earth elements on Sr isotopic analysis using multi-collector inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Yang, Yue-Heng; Wu, Fu-Yuan; Xie, Lie-Wen; Chu, Zhu-Yin; Yang, Jin-Hui

    2014-07-01

    We re-evaluate the interference of doubly charged heavy rare earth elements during Sr isotopic analysis using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). A series of mixed solutions of standard reference material SRM 987, rare earth elements, and Sr separated from rock reference materials are measured to assess the influence of isobaric interferences on the MC-ICP-MS analysis of Sr isotopes. After sample dissolution, conventional cation-exchange chromatography is employed for Sr purification of rock reference materials prior to MC-ICP-MS measurement. It has been demonstrated that if the natural abundances of Er and Yb are used to correct for doubly charged ion interferences on Sr, an overcorrection results. In contrast, the use of measured doubly charged ion ratios results in an accurate and precise correction of isobaric interference. This finding is confirmed by analytical results for several certified reference materials from mafic (basaltic) to felsic (granitic) silicate rocks. It is noteworthy that, because Er is more prone to doubly charged ion formation, it dominates over Yb doubly charged ions as an interference source.

  16. ANALYSIS OF RICIN TOXIN PREPARATIONS FOR CARBOHYDRATE AND FATTY ACID ABUNDANCE AND ISOTOPE RATIO INFORMATION

    SciTech Connect

    Wunschel, David S.; Kreuzer-Martin, Helen W.; Antolick, Kathryn C.; Colburn, Heather A.; Moran, James J.; Melville, Angela M.

    2009-12-01

    This report describes method development and preliminary evaluation for analyzing castor samples for signatures of purifying ricin. Ricin purification from the source castor seeds is essentially a problem of protein purification using common biochemical methods. Indications of protein purification will likely manifest themselves as removal of the non-protein fractions of the seed. Two major, non-protein, types of biochemical constituents in the seed are the castor oil and various carbohydrates. The oil comprises roughly half the seed weight while the carbohydrate component comprises roughly half of the remaining “mash” left after oil and hull removal. Different castor oil and carbohydrate components can serve as indicators of specific toxin processing steps. Ricinoleic acid is a relatively unique fatty acid in nature and is the most abundant component of castor oil. The loss of ricinoleic acid indicates a step to remove oil from the seeds. The relative amounts of carbohydrates and carbohydrate-like compounds, including arabinose, xylose, myo-inositol fucose, rhamnose, glucosamine and mannose detected in the sample can also indicate specific processing steps. For instance, the differential loss of arabinose relative to mannose and N-acetyl glucosamine indicates enrichment for the protein fraction of the seed using protein precipitation. The methods developed in this project center on fatty acid and carbohydrate extraction from castor samples followed by derivatization to permit analysis by gas chromatography-mass spectrometry (GC-MS). Method descriptions herein include: the source and preparation of castor materials used for method evaluation, the equipment and description of procedure required for chemical derivatization, and the instrument parameters used in the analysis. Two types of derivatization methods describe analysis of carbohydrates and one procedure for analysis of fatty acids. Two types of GC-MS analysis is included in the method development, one

  17. Fast and accurate analysis of large-scale composite structures with the parallel multilevel fast multipole algorithm.

    PubMed

    Ergül, Özgür; Gürel, Levent

    2013-03-01

    Accurate electromagnetic modeling of complicated optical structures poses several challenges. Optical metamaterial and plasmonic structures are composed of multiple coexisting dielectric and/or conducting parts. Such composite structures may possess diverse values of conductivities and dielectric constants, including negative permittivity and permeability. Further challenges are the large sizes of the structures with respect to wavelength and the complexities of the geometries. In order to overcome these challenges and to achieve rigorous and efficient electromagnetic modeling of three-dimensional optical composite structures, we have developed a parallel implementation of the multilevel fast multipole algorithm (MLFMA). Precise formulation of composite structures is achieved with the so-called "electric and magnetic current combined-field integral equation." Surface integral equations are carefully discretized with piecewise linear basis functions, and the ensuing dense matrix equations are solved iteratively with parallel MLFMA. The hierarchical strategy is used for the efficient parallelization of MLFMA on distributed-memory architectures. In this paper, fast and accurate solutions of large-scale canonical and complicated real-life problems, such as optical metamaterials, discretized with tens of millions of unknowns are presented in order to demonstrate the capabilities of the proposed electromagnetic solver. PMID:23456127

  18. An analytical system for stable isotope analysis on carbon monoxide using continuous-flow isotope-ratio mass spectrometry

    NASA Astrophysics Data System (ADS)

    Pathirana, S. L.; van der Veen, C.; Popa, M. E.; Röckmann, T.

    2015-12-01

    A fully automated system for the determination of δ13C and δ18O in atmospheric CO has been developed. CO is extracted from an air sample and converted into carbon dioxide (CO2) using the Schütze reagent. The isotopic composition is determined with an isotope-ratio mass spectrometer (IRMS) technique. The entire system is continuously flushed with high-purity helium (He), the carrier gas. The blank signal of the Schütze reagent is ~ 4 nmol mol-1, or 1-3 % of the typical sample size. The repeatability is 0.1 ‰ for δ13C and 0.2 ‰ for δ18O. The peak area allows for simultaneous determination of the mole fraction with an analytical repeatability of ~ 0.7 nmol mol-1 for 100 mL of ambient air (185.4 nmol mol-1 of CO). An automated single measurement is performed in only 18 min, and the achieved time efficiency (and small volume of sample air) allows for repetitive measurements practically.

  19. Stable isotope analysis and satellite tracking reveal interspecific resource partitioning of nonbreeding albatrosses off Alaska

    USGS Publications Warehouse

    Suryan, R.M.; Fischer, K.N.

    2010-01-01

    Albatrosses (Diomedeidae) are the most threatened family of birds globally. The three North Pacific species (Phoebastria Reichenbach, 1853) are listed as either endangered or vulnerable, with the population of Short-tailed Albatross (Phoebastria albatrus (Pallas, 1769)) less than 1% of its historical size. All North Pacific albatross species do not currently breed sympatrically, yet they do co-occur at-sea during the nonbreeding season. We incorporated stable isotope analysis with the first simultaneous satellite-tracking study of all three North Pacific albatross species while sympatric on summer (nonbreeding season) foraging grounds off Alaska. Carbon isotope ratios and tracking data identify differences in primary foraging domains of continental shelf and slope waters for Short-tailed Albatrosses and Black-footed Albatrosses (Phoebastria nigripes (Audubon, 1839)) versus oceanic waters for Laysan Albatrosses (Phoebastria immutabilis (Roths-child, 1893)). Short-tailed and Black-footed albatrosses also fed at higher trophic levels than Laysan Albatrosses. The relative trophic position of Black-footed and Laysan albatrosses, however, appears to differ between nonbreeding and breeding seasons. Spatial segregation also occurred at a broader geographic scale, with Short-tailed Albatrosses ranging more north into the Bering Sea than Black-footed Albatrosses, which ranged more to the southeast, and Laysan Albatrosses more to the southwest. Differences in carbon isotope ratios among North Pacific albatross species during the nonbreeding season likely reflect the relative proportion of neritic (more carbon enriched) versus oceanic (carbon depleted) derived nutrients, and possible differential use of fishery discards, rather than latitudinal differences in distribution.

  20. A soil water distillation technique using He-purging for stable isotope analysis

    NASA Astrophysics Data System (ADS)

    Ignatev, A.; Velivetckaia, T.; Sugimoto, A.; Ueta, A.

    2013-08-01

    A new method of soil water extraction for oxygen and hydrogen isotopic analysis has been developed; this method uses a helium flow system as an alternative to the conventional vacuum extraction method. The method significantly increases the efficiency of sample preparation and simplifies the extraction. During the water distillation, a helium carrier gas transfers water vaporized at 95 °C from the soil sample to a cold trap at liquid nitrogen temperature. An extraction time of 180 min is used to distill the water from the fine-grained soil completely. The proposed He-purging distillation technique makes it possible to distill approximately a dozen samples simultaneously. The method was tested using liquid water samples and clayey soil samples hydrated with water of known isotopic composition. The standard deviations for these tests were 0.08‰ for δ18O and 0.7‰ for δD. An intercomparison test was conducted for the helium and vacuum extraction methods using natural soil samples. The correlation coefficients between the methods were 0.9926 and 0.9939 for δD and δ18O, respectively. The proposed He-purging distillation method can achieve high precision for clayey soil samples with low water content and has the potential to provide adequate isotopic data in hydrological and ecological studies. The method is relatively fast, efficient, and inexpensive. We also recommend using the method to distill salt solutions (sea water, mineralized water) before determining the δD and δ18O values using a chromium or carbon reduction method to avoid “salt effects”.

  1. Compound specific stable isotope analysis (CSIA) to characterize transformation mechanisms of α-hexachlorocyclohexane.

    PubMed

    Zhang, Ning; Bashir, Safdar; Qin, Jinyi; Schindelka, Janine; Fischer, Anko; Nijenhuis, Ivonne; Herrmann, Hartmut; Wick, Lukas Y; Richnow, Hans H

    2014-09-15

    A systematic investigation of environmentally relevant transformation processes of alpha-hexachlorocyclohexane (α-HCH) was performed in order to explore the potential of compound specific stable isotope analysis (CSIA) to characterize reaction mechanisms. The carbon isotope enrichment factors (ɛC) for the chemical transformations of α-HCH via direct photolysis, indirect photolysis (UV/H2O2), hydrolysis, electro-reduction or reduction by Fe(0) were quantified and compared to those previously published for biodegradation. Hydrogen abstraction by hydroxyl radicals generated by UV/H2O2 led to ɛC of -1.9 ± 0.2 ‰ with an apparent kinetic carbon isotope effect (AKIEC) of 1.012 ± 0.001. Dehydrochlorination by alkaline hydrolysis yielded ɛC of -7.6 ± 0.4 ‰ with AKIEC of 1.048 ± 0.003. Dechlorination either by homolytic bond cleavage in direct photolysis (ɛC=-2.8 ± 0.2 ‰) or single-electron transfer in electro-reduction (ɛC=-3.8 ± 0.4 ‰) corresponded to AKIEC of 1.017 ± 0.001 and 1.023 ± 0.003, respectively. Dichloroelimination catalyzed by Fe(0) via two-electron transfers resulted in ɛC of -4.9 ± 0.1 ‰. AKIEC values assuming either a concerted or a stepwise mechanism were 1.030 ± 0.0006 and 1.015 ± 0.0003, respectively. Contrary to biodegradation, no enantioselectivity of α-HCH was observed in chemical reactions, which might be used to discriminate chemical and biological in situ transformations. PMID:25238192

  2. Trophic size-structure of sailfish Istiophorus platypterus in eastern Taiwan estimated by stable isotope analysis.

    PubMed

    Tsai, C-N; Chiang, W-C; Sun, C-L; Shao, K-T; Chen, S-Y; Yeh, S-Z

    2014-02-01

    To examine trophic dynamics over different size classes, an isotopic study of sailfish Istiophorus platypterus life-history stages was carried out. Samples were collected from eastern Taiwan and the South China Sea during April 2009 and February 2012. A total of 263 samples (111-245 cm, lower jaw fork length, LLJFL ) were examined for changes in trophic structure in relation to LLJFL by using stable isotope analysis of carbon (δ(13) C) and nitrogen (δ(15) N). The δ(15) N values for I. platypterus ranged from 7·51 to 14·19‰ (mean ± s.d. = 12·06 ± 1·16‰) and the δ(13) C values ranged from -22·04 to -15·48‰ (mean ± s.d. = -17·62 ± 1·10‰). The δ(15) N values were positively dependent on LLJFL (r(2)  = 0·377), whereas δ(13) C were negatively dependent on LLJFL (r(2)  = 0·063). There were significantly different seasonal changes in nitrogen and carbon isotopic concentration, but no significant differences in concentrations between eastern Taiwan and the South China Sea were reported. The trophic level (TL ) of each LLJFL class was correlated, starting from 2·84 TL for size class I (LLJFL  < 140 cm) and reaching 5·03 TL for size class VI (LLJFL > 221 cm). The mean ± s.d. TL was 4·43 ± 0·19 for all samples. The results reveal that I. platypterus occupies a wide range of trophic levels and different size classes occupy different trophic positions in the pelagic ecosystem. PMID:24447322

  3. COMPOUND-SPECIFIC STABLE ISOTOPE ANALYSIS TO DEMONSTRATE IN-SITU MTBE BIOTRANSFORMATION

    EPA Science Inventory

    Change of stable isotope composition of organic contaminants (isotopic fractionation) is a useful indicator of biotransformation. Most of applications to date are in the area of chlorinated solvents and recently BTEX, MTBE and TBA. Chemical reactions (biotic- and abiotic transfor...