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Sample records for isotope mass spectrometry

  1. Solvent Extraction, Ion Chromatography, and Mass Spectrometry of Molybdenum Isotopes

    E-print Network

    Solvent Extraction, Ion Chromatography, and Mass Spectrometry of Molybdenum Isotopes Nicolas-le`s-Nancy Cedex, France A procedure was developed that allows precise determi- nation of molybdenum isotope abundances in natural samples. Purification of molybdenum was first achieved by solvent extraction using di(2

  2. MASS SPECTROMETRY AND NATURAL VARIATIONS OF IRON ISOTOPES

    E-print Network

    -ablation multi-collection inductively coupled plasma mass spectrometry (LA-MC-ICPMS, Hirata & Ohno, 2001) have not require high precision. The recent advent of multi-collection inductively coupled plasma mass attempts to measure the stable isotopic composition of Fe relied on thermal ionization mass spectrometers

  3. Discrepancies between isotope ratio infrared spectroscopy and isotope ratio mass spectrometry for the

    E-print Network

    Goldsmith, Greg

    Discrepancies between isotope ratio infrared spectroscopy and isotope ratio mass spectrometry for the stable isotope analysis of plant and soil waters Adam G. West1,2*, Gregory R. Goldsmith1 , Paul D. Brooks Center for Stable Isotope Biogeochemistry, University of California, Berkeley, Berkeley, CA 94720, USA

  4. Calibration graphs in isotope dilution mass spectrometry.

    PubMed

    Pagliano, Enea; Mester, Zoltán; Meija, Juris

    2015-10-01

    Isotope-based quantitation is routinely employed in chemical measurements. Whereas most analysts seek for methods with linear theoretical response functions, a unique feature that distinguishes isotope dilution from many other analytical methods is the inherent possibility for a nonlinear theoretical response curve. Most implementations of isotope dilution calibration today either eliminate the nonlinearity by employing internal standards with markedly different molecular weight or they employ empirical polynomial fits. Here we show that the exact curvature of any isotope dilution curve can be obtained from three-parameter rational function, y = f(q) = (a0 + a1q)/(1 + a2q), known as the Padé[1,1] approximant. The use of this function allows eliminating an unnecessary source of error in isotope dilution analysis when faced with nonlinear calibration curves. In addition, fitting with Padé model can be done using linear least squares. PMID:26481988

  5. Mass spectrometry and isotopes: a century of research and discussion.

    PubMed

    Budzikiewicz, Herbert; Grigsby, Ronald D

    2006-01-01

    In 1815, the British physician William Prout had advanced the theory that the molecular masses of elements were multiples of the mass of hydrogen. This "whole number rule" (and especially deviations from it) played an important role in the discussion whether elements could be mixtures of isotopes. F. Soddy's discovery (1910) that lead obtained by decay of uranium and of thorium differed in mass was considered a peculiarity of radioactive materials. The question of the existence of isotopes came up when the instruments developed by J.J. Thomson and by W. Wien to study cathode and canal rays by deflection in electric and magnetic fields were steadily improved. In 1913, Thomson mentioned a weak line at mass 22 accompanying the expected one at mass 20 when he analyzed the mass spectrum of neon. Subsequently Aston obtained the mass spectrum of chlorine with masses at 35 and 37. Still in 1921, Thomson objected heavily to the idea of isotopes. The isotope problem was finally settled, but more accurate mass measurements showed that even isotopic weights differed to some extent from the whole numbers. Based on earlier ideas of P. Langevin and J.-L. Costa, F.W. Aston and A.J. Dempster developed the idea of packing fractions and mass defects due to the transformation of a portion of the matter comprising the atomic nucleus into energy. While the determination of the exact isotopic masses had improved over the years, the accurate determination of isotopic abundances remained a problem as long as photographic recording was used. Here especially A.O. Nier pioneered using dual collectors and compensation measurements. This was the prerequisite for the discovery that isotopic ratios varied somewhat in nature. M. Dole discovered the fractionation of oxygen isotopes by photosynthesis and respiration. Today 13C/12C-ratios are employed to detect adulterations of food and in doping analysis, and 14C/13C-ratios obtained by accelerator mass spectrometry are used for dating historical objects, just to give some examples. PMID:16134128

  6. Mass spectrometry.

    NASA Technical Reports Server (NTRS)

    Burlingame, A. L.; Johanson, G. A.

    1972-01-01

    Review of the current state of mass spectrometry, indicating its unique importance for advanced scientific research. Mass spectrometry applications in computer techniques, gas chromatography, ion cyclotron resonance, molecular fragmentation and ionization, and isotope labeling are covered. Details are given on mass spectrometry applications in bio-organic chemistry and biomedical research. As the subjects of these applications are indicated alkaloids, carbohydrates, lipids, terpenes, quinones, nucleic acid components, peptides, antibiotics, and human and animal metabolisms. Particular attention is given to the mass spectra of organo-inorganic compounds, inorganic mass spectrometry, surface phenomena such as secondary ion and electron emission, and elemental and isotope analysis. Further topics include mass spectrometry in organic geochemistry, applications in geochronology and cosmochemistry, and organic mass spectrometry.

  7. Automated spike preparation system for Isotope Dilution Mass Spectrometry (IDMS)

    SciTech Connect

    Maxwell, S.L. III; Clark, J.P.

    1990-12-31

    Isotope Dilution Mass Spectrometry (IDMS) is a method frequently employed to measure dissolved, irradiated nuclear materials. A known quantity of a unique isotope of the element to be measured (referred to as the ``spike``) is added to the solution containing the analyte. The resulting solution is chemically purified then analyzed by mass spectrometry. By measuring the magnitude of the response for each isotope and the response for the ``unique spike`` then relating this to the known quantity of the ``spike``, the quantity of the nuclear material can be determined. An automated spike preparation system was developed at the Savannah River Site (SRS) to dispense spikes for use in IDMS analytical methods. Prior to this development, technicians weighed each individual spike manually to achieve the accuracy required. This procedure was time-consuming and subjected the master stock solution to evaporation. The new system employs a high precision SMI Model 300 Unipump dispenser interfaced with an electronic balance and a portable Epson HX-20 notebook computer to automate spike preparation.

  8. Improved Isotopic Measurement of Plutonium by Thermal Ionization Mass Spectrometry

    SciTech Connect

    Shick, C. Jr.

    2002-02-07

    Thermal ionization mass spectrometry (TIMS) is accepted widely as the benchmark method for precise and accurate isotopic determination of plutonium. TIMS is one of the few analytical methods capable of determining Pu in bioassay samples at the level required for detecting a 50 yr committed dose of 100 mRem resulting from an inhalation exposure to highly insoluble forms of Pu. Typically, Pu is measured in bioassay samples by radiochemical separation, electrodeposition onto a planchet, and radiometric determination by alpha spectrometry. If, based on the alpha spectrometry results, a sample is deemed to need a more sensitive analysis (i.e. suspected uptake, borderline alpha spectrometry positive for Pu uptake, etc.), then the sample is prepared for analysis by TIMS. Part of the development process for establishing a program to determine Pu in bioassay samples by TIMS at the Savannah River Site involved a careful evaluation of the Pu blank value in the reagents used for sample preparation and in urine blanks. This exercise allowed for the evaluation of the newly developed radiochemical separation procedure, the resin bead loading procedure, and the detection limits of the thermal ionization mass spectrometer.

  9. 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 separations. The system couples a high-resolution ion mobility (IM) drift cell to the front end of a mass spectrometer (MS) allowing for chemical separation prior to isotope distribution analyses. This will yield isotope ratio measurement capabilities with minimal sample preparation.

  10. High Precision Isotope Petrography by Secondary Ion Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Yurimoto, H.

    2009-12-01

    Since Shimizu et al. (GCA 1978) have demonstrated that in-situ micro-scale analyses of isotopes and trace elements in minerals were succeeded by secondary ion mass spectrometry (SIMS), geochemists develop the SIMS methods towards isotope mapping with spatial resolution of electron microscopy level. At present, high spatial resolution imaging by SIMS has been succeeded by scanning methods using ion-probe and by projection methods using stigmatic secondary ion optics. For high precision isotope analysis with high spatial resolution, intense secondary ions are indispensable for each pixel in the image. However, one of the major instrumental problems is that there were no adequate detectors for this purpose. In order to solve the problem, we proposed a two-dimensional solid-state ion detector called SCAPS (Takayanagi et al., IEEE Trans. 2003). The development is still continued and performances of recent SCAPS detector is achieved to: (1) direct sensitive for ions from single ion, (2) no dead time, and (3) perfect linearity of five orders of magnitude dynamic range. Installing the SCAPS detector into a stigmatic SIMS of Cameca ims-1270, we obtained oxygen isotope (delta-O-17 and delta-O-18) images of about 100 micrometer field with ~500 nm resolution and ~5 permil precision. The performance of high precision isotope imaging have might not be matured, but overcome a hurdle towards isotope petrography (Isotopography). We apply this isotopography to research fields of (a) survey of isotope anomalous micrograins and (b) isotope micro-distribution in rocks and minerals. In the application (a), we found in-situ presolar grains in meteorites (Nagashima et al., Nature 2004) and cosmic symplectite (COS) from a meteorite (Sakamoto et al., Science 2007). In the application (b), we showed how distribute oxygen isotopic compositions in micro-scale within CAI minerals (Yurimoto et al., Rev. Mineral. 2008; Fagan et al., in prep.). In combination fields of (a) and (b), we demonstrated how preserves Martian water and how contaminates terrestrial water in Martian meteorites (Greenwood et al., GRL 2008). These new knowledge from isotopography provides novel perspective of earth and planetary sciences.

  11. Quantitation of DNA adducts by stable isotope dilution mass spectrometry

    PubMed Central

    Tretyakova, Natalia; Goggin, Melissa; Janis, Gregory

    2012-01-01

    Exposure to endogenous and exogenous chemicals can lead to the formation of structurally modified DNA bases (DNA adducts). If not repaired, these nucleobase lesions can cause polymerase errors during DNA replication, leading to heritable mutations potentially contributing to the development of cancer. Due to their critical role in cancer initiation, DNA adducts represent mechanism-based biomarkers of carcinogen exposure, and their quantitation is particularly useful for cancer risk assessment. DNA adducts are also valuable in mechanistic studies linking tumorigenic effects of environmental and industrial carcinogens to specific electrophilic species generated from their metabolism. While multiple experimental methodologies have been developed for DNA adduct analysis in biological samples – including immunoassay, HPLC, and 32P-postlabeling – isotope dilution high performance liquid chromatography-electrospray ionization-tandem mass spectrometry (HPLC-ESI-MS/MS) generally has superior selectivity, sensitivity, accuracy, and reproducibility. As typical DNA adducts concentrations in biological samples are between 0.01 – 10 adducts per 108 normal nucleotides, ultrasensitive HPLC-ESI-MS/MS methodologies are required for their analysis. Recent developments in analytical separations and biological mass spectrometry – especially nanoflow HPLC, nanospray ionization MS, chip-MS, and high resolution MS – have pushed the limits of analytical HPLC-ESI-MS/MS methodologies for DNA adducts, allowing researchers to accurately measure their concentrations in biological samples from patients treated with DNA alkylating drugs and in populations exposed to carcinogens from urban air, drinking water, cooked food, alcohol, and cigarette smoke. PMID:22827593

  12. Iron-Isotopic Fractionation Studies Using Multiple Collector Inductively Coupled Plasma Mass Spectrometry

    NASA Technical Reports Server (NTRS)

    Anbar, A. D.; Zhang, C.; Barling, J.; Roe, J. E.; Nealson, K. H.

    1999-01-01

    The importance of Fe biogeochemistry has stimulated interest in Fe isotope fractionation. Recent studies using thermal ionization mass spectrometry (TIMS) and a "double spike" demonstrate the existence of biogenic Fe isotope effects. Here, we assess the utility of multiple-collector inductively-coupled plasma mass spectrometry(MC-ICP-MS) with a desolvating sample introduction system for Fe isotope studies, and present data on Fe biominerals produced by a thermophilic bacterium. Additional information is contained in the original extended abstract.

  13. Isotope Dilution Mass Spectrometry for the Quantification of Sulfane Sulfurs

    PubMed Central

    Liu, Chunrong; Zhang, Faya; Munske, Gerhard; Zhang, Hui

    2014-01-01

    Sulfane sulfurs are one type of important reactive sulfur species. These molecules have unique reactivity that can attach reversibly to other sulfur atoms and exhibit regulatory effects in diverse biological systems. Recent studies have suggested that sulfane sulfurs are involved in signal transduction processes regulated by hydrogen sulfide (H2S). Accurate and reliable measurements of sulfane sulfurs in biological samples are thus needed to reveal their production and mechanisms of actions. Herein we report a convenient and accurate method for the determination of sulfane sulfurs concentrations. The method employs a triphenylphosphine derivative (P2) to capture sulfane sulfurs as a stable phosphine sulphide product PS2. The concentration of PS2 was then determined by isotope dilution mass spectrometry, using a 13C3-labelled phosphine sulfide PS1 as the internal standard. The specificity and efficiency of the method were proved by model reactions. It was also applied in the measurement of sulfane sulfurs in mice tissues including brain, kidney, lung, liver, heart, spleen, and blood. PMID:25152234

  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. Isotope Ratio Monitoring Gas Chromatography Mass Spectrometry (IRM-GCMS)

    NASA Technical Reports Server (NTRS)

    Freeman, K. H.; Ricci, S. A.; Studley, A.; Hayes, J. M.

    1989-01-01

    On Earth, the C-13 content of organic compounds is depleted by roughly 13 to 23 permil from atmospheric carbon dioxide. This difference is largely due to isotope effects associated with the fixation of inorganic carbon by photosynthetic organisms. If life once existed on Mars, then it is reasonable to expect to observe a similar fractionation. Although the strongly oxidizing conditions on the surface of Mars make preservation of ancient organic material unlikely, carbon-isotope evidence for the existence of life on Mars may still be preserved. Carbon depleted in C-13 could be preserved either in organic compounds within buried sediments, or in carbonate minerals produced by the oxidation of organic material. A technique is introduced for rapid and precise measurement of the C-13 contents of individual organic compounds. A gas chromatograph is coupled to an isotope-ratio mass spectrometer through a combustion interface, enabling on-line isotopic analysis of isolated compounds. The isotope ratios are determined by integration of ion currents over the course of each chromatographic peak. Software incorporates automatic peak determination, corrections for background, and deconvolution of overlapped peaks. Overall performance of the instrument was evaluated by the analysis of a mixture of high purity n-alkanes of know isotopic composition. Isotopic values measured via IRM-GCMS averaged withing 0.55 permil of their conventionally measured values.

  16. Attogram measurement of rare isotopes by CW resonance ionization mass spectrometry

    SciTech Connect

    Bushaw, B.A.

    1992-05-01

    Three-color double-resonance ionization mass spectrometry, using two single-frequency cw dye lasers and a cw carbon dioxide laser, has been applied to the detection of attogram quantities of rare radionuclides. {sup 210}Pb has been measured in human hair and brain tissue samples to assess indoor radon exposure. Measurements on {sup 90}Sr have shown overall isotopic selectivity of greater than 10{sup 9} despite unfavorable isotope shifts relative to the major stable isotope, {sup 88}Sr.

  17. DETERMINATION OF NIACIN IN FOOD MATERIALS BY ISOTOPE DILUTION MASS SPECTROMETRY

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The availability of deuterium-labeled nicotinic acid makes stable isotope dilution mass spectrometry (SIDMS) coupled with liquid chromatography (LC) an attractive option for the determination of the water-soluble B-vitamin, niacin, in food samples. We present a method based on acid digestion, solid ...

  18. Protein N- and C-Termini Identification Using Mass Spectrometry and Isotopic Labeling

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A new method for protein N- and C-terminal analysis using mass spectrometry is introduced. A novel stable isotopic labeling scheme has been developed to identify terminal peptides generated from an enzyme digestion for the determination of both N- and C-termini of the protein. This method works dire...

  19. Mass spectrometry and natural variations of iron isotopes.

    PubMed

    Dauphas, Nicolas; Rouxel, Olivier

    2006-01-01

    Although the processes that govern iron isotope variations in nature are just beginning to be understood, multiple studies attest of the virtue of this system to solve important problems in geosciences and biology. In this article, we review recent advances in the geochemistry, cosmochemistry, and biochemistry of iron isotopes. In Section 2, we briefly address the question of the nucleosynthesis of Fe isotopes. In Section 3, we describe the different methods for purifying Fe and analyzing its isotopic composition. The methods of SIMS, RIMS, and TIMS are presented but more weight is given to measurements by MC-ICPMS. In Section 4, the isotope anomalies measured in extraterrestrial material are briefly discussed. In Section 5, we show how high temperature processes like evaporation, condensation, diffusion, reduction, and phase partitioning can affect Fe isotopic composition. In Section 6, the various low temperature processes causing Fe isotopic fractionation are presented. These involve aqueous and biologic systems. PMID:16463281

  20. On the Fine Isotopic Distribution and Limits to Resolution in Mass Spectrometry.

    PubMed

    Dittwald, Piotr; Valkenborg, Dirk; Claesen, Jürgen; Rockwood, Alan L; Gambin, Anna

    2015-10-01

    Mass spectrometry enables the study of increasingly larger biomolecules with increasingly higher resolution, which is able to distinguish between fine isotopic variants having the same additional nucleon count, but slightly different masses. Therefore, the analysis of the fine isotopic distribution becomes an interesting research topic with important practical applications. In this paper, we propose the comprehensive methodology for studying the basic characteristics of the fine isotopic distribution. Our approach uses a broad spectrum of methods ranging from generating functions-that allow us to estimate the variance and the information theory entropy of the distribution-to the theory of thermal energy fluctuations. Having characterized the variance, spread, shape, and size of the fine isotopic distribution, we are able to indicate limitations to high resolution mass spectrometry. Moreover, the analysis of "thermorelativistic" effects (i.e., mass uncertainty attributable to relativistic effects coupled with the statistical mechanical uncertainty of the energy of an isolated ion), in turn, gives us an estimate of impassable limits of isotopic resolution (understood as the ability to distinguish fine structure peaks), which can be moved further only by cooling the ions. The presented approach highlights the potential of theoretical analysis of the fine isotopic distribution, which allows modeling the data more accurately, aiming to support the successful experimental measurements. Graphical Abstract ?. PMID:26265039

  1. On the Fine Isotopic Distribution and Limits to Resolution in Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Dittwald, Piotr; Valkenborg, Dirk; Claesen, Jürgen; Rockwood, Alan L.; Gambin, Anna

    2015-08-01

    Mass spectrometry enables the study of increasingly larger biomolecules with increasingly higher resolution, which is able to distinguish between fine isotopic variants having the same additional nucleon count, but slightly different masses. Therefore, the analysis of the fine isotopic distribution becomes an interesting research topic with important practical applications. In this paper, we propose the comprehensive methodology for studying the basic characteristics of the fine isotopic distribution. Our approach uses a broad spectrum of methods ranging from generating functions—that allow us to estimate the variance and the information theory entropy of the distribution—to the theory of thermal energy fluctuations. Having characterized the variance, spread, shape, and size of the fine isotopic distribution, we are able to indicate limitations to high resolution mass spectrometry. Moreover, the analysis of "thermorelativistic" effects (i.e., mass uncertainty attributable to relativistic effects coupled with the statistical mechanical uncertainty of the energy of an isolated ion), in turn, gives us an estimate of impassable limits of isotopic resolution (understood as the ability to distinguish fine structure peaks), which can be moved further only by cooling the ions. The presented approach highlights the potential of theoretical analysis of the fine isotopic distribution, which allows modeling the data more accurately, aiming to support the successful experimental measurements.

  2. Illustrating the Concepts of Isotopes and Mass Spectrometry in Introductory Courses: A MALDI-TOF Mass Spectrometry Laboratory Experiment

    ERIC Educational Resources Information Center

    Dopke, Nancy Carter; Lovett, Timothy Neal

    2007-01-01

    Mass spectrometry is a widely used and versatile tool for scientists in many different fields. Soft ionization techniques such as matrix-assisted laser desorption/ionization (MALDI) allow for the analysis of biomolecules, polymers, and clusters. This article describes a MALDI mass spectrometry experiment designed for students in introductory…

  3. In-Vivo Zinc Metabolism by Isotope Ratio Mass Spectrometry

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The purpose of this chapter is to highlight some of the methodological and technical issues surrounding the in vivo use of stable isotopes and to provide examples of how such studies have advanced our knowledge of human zinc metabolism. The advantages and disadvantages of the currently available in...

  4. RAPID DETERMINATION OF 237 NP AND PU ISOTOPES IN WATER BY INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY AND ALPHA SPECTROMETRY

    SciTech Connect

    Maxwell, S.; Jones, V.; Culligan, B.; Nichols, S.; Noyes, G.

    2010-06-23

    A new method that allows rapid preconcentration and separation of plutonium and neptunium in water samples was developed for the measurement of {sup 237}Np and Pu isotopes by inductively-coupled plasma mass spectrometry (ICP-MS) and alpha spectrometry; a hybrid approach. {sup 238}U can interfere with {sup 239}Pu measurement by ICP-MS as {sup 238}UH{sup +} mass overlap and {sup 237}Np via peak tailing. The method provide enhanced removal of uranium by separating Pu and Np initially on TEVA Resin, then moving Pu to DGA resin for additional removal of uranium. The decontamination factor for uranium from Pu is almost 100,000 and the decontamination factor for U from Np is greater than 10,000. This method uses stacked extraction chromatography cartridges and vacuum box technology to facilitate rapid separations. Preconcentration is performed using a streamlined calcium phosphate precipitation method. Purified solutions are split between ICP-MS and alpha spectrometry so that long and short-lived Pu isotopes can be measured successfully. The method allows for simultaneous extraction of 20 samples (including QC samples) in 4 to 6 hours, and can also be used for emergency response. {sup 239}Pu, {sup 242}Pu and {sup 237}Np were measured by ICP-MS, while {sup 236}Pu, {sup 238}Pu, and {sup 239}Pu were measured by alpha spectrometry.

  5. Otolith oxygen isotopes measured by high-precision secondary ion mass spectrometry reflect life history of a yellowfin sole

    E-print Network

    Meyers, Stephen R.

    Otolith oxygen isotopes measured by high-precision secondary ion mass spectrometry reflect life: The oxygen isotope ratio (d18 O value) of aragonite fish otoliths is dependent on the temperature and the d18-digestion techniques for stable isotope analysis of otoliths, especially given their compact nature. METHODS: High

  6. Performance and limits of liquid chromatography isotope ratio mass spectrometry system for halogenated compounds

    NASA Astrophysics Data System (ADS)

    Gilevska, Tetyana; Gehre, Matthias; Richnow, Hans

    2014-05-01

    Compound Specific Isotope Analysis (CSIA) has been an important step for the assessment of the origin and fate of compounds in environmental science.[1] Biologically or pharmaceutically important compounds often are not amenable for gas chromatographic separation because of high polarity and lacking volatility, thermostability. In 2004 liquid chromatography isotope ratio mass spectrometry (LC-IRMS) became commercially available. LC-IRMS system intent a quantitative conversion of analytes separation into CO2 via wet oxidation with sodium persulfate in the presence of phosphoric acid while analytes are still dissolved in the aqueous liquid phase.[2] The aim of this study is to analyze the oxidation capacity of the interface of the LC-IRMS system and determine which parameters could improve oxidation of compounds which are resistant to persulfate oxidation. Oxidation capacity of the liquid chromatography isotope ratio mass spectrometry system was tested with halogenated acetic acid and a set of aromatic compounds with different substitutes. Acetic acid (AA) was taken as a model compound for complete oxidation and compared to the oxidation of other analytes on a molar basis. Correct values were obtained for di- and mono chlorinated and fluorinated and also for tribrominated acetic acid and for all studied aromatic compounds. Incomplete oxidation for trichloroacetic (TCAA) and trifluoroacetic (TFAA) acid was revealed with lower recovery compared to acetic acid and isotope fractionation leading to depleted carbon isotope composition compared to values obtained with an elementary analyzer connected to an isotope mass spectrometer Several optimization steps were tried in order to improve the oxidation of TCAA and TFAA: (i) increasing the concentration of the oxidizing agent, (ii) variation of flow rate of the oxidizing and acid solution, (iii) variation of flow rate of liquid chromatography pump (iv) addition of a catalyzer. These modifications lead to longer reaction time in the coil and increase in the concentration of radical but complete combustion of highly chlorinated or fluorinated compounds was not achieved. Due to these findings the limit for a LC-IRMS system for similar structure compounds can be predicted. 1. Elsner, M., et al., Current challenges in compound-specific stable isotope analysis of environmental organic contaminants. Analytical and Bioanalytical Chemistry, 2012. 403(9): p. 2471-2491. 2. Krummen, M., et al., A new concept for isotope ratio monitoring liquid chromatography/mass spectrometry. Rapid Communications in Mass Spectrometry, 2004. 18(19): p. 2260-2266.

  7. Improving precision in resonance ionization mass spectrometry : influence of laser bandwidth in uranium isotope ratio measurements.

    SciTech Connect

    Isselhardt, B. H.; Savina, M. R.; Knight, K. B.; Pellin, M. J.; Hutcheon, I. D.; Prussin, S. G.

    2011-03-01

    The use of broad bandwidth lasers with automated feedback control of wavelength was applied to the measurement of {sup 235}U/{sup 238}U ratios by resonance ionization mass spectrometry (RIMS) to decrease laser-induced isotopic fractionation. By broadening the bandwidth of the first laser in a three-color, three-photon ionization process from a bandwidth of 1.8 GHz to about 10 GHz, the variation in sequential relative isotope abundance measurements decreased from 10% to less than 0.5%. This procedure was demonstrated for the direct interrogation of uranium oxide targets with essentially no sample preparation.

  8. High-precision gas chromatography-combustion isotope ratio mass spectrometry at low signal levels.

    PubMed

    Goodman, K J; Brenna, J T

    1995-01-01

    Precision and accuracy of gas chromatography-combustion isotope ratio mass spectrometry are investigated for sample levels down to about 5 pmol C in fatty acid methyl ester mixtures spanning 1000-fold in concentration. Precision and accuracy of isotope ratios diverge rapidly for conventional summation methods, and become unusable below 30 pmol material on column. At lower levels, mean isotope ratios were statistically different from reference values indicating bias as well as poor precision. In contrast, curve fitting, using the exponentially modified Gaussian line shape, gives improved precision for most peaks and useful results down to 3 pmol. The curve-fitting algorithm was also less sensitive to signal integration time than the summation method. These data indicate that curve fitting may be the method of choice for integration of noisy data when high-precision isotope ratios are desired. PMID:7881535

  9. Calibration and Data Processing in Gas Chromatography Combustion Isotope Ratio Mass Spectrometry

    PubMed Central

    Zhang, Ying; Tobias, Herbert J.; Sacks, Gavin L.; Brenna, J. Thomas

    2013-01-01

    Compound-specific isotope analysis (CSIA) by gas chromatography combustion isotope ratio mass spectrometry (GCC-IRMS) is a powerful technique for the sourcing of substances, such as determination of the geographic or chemical origin of drugs and food adulteration, and it is especially invaluable as a confirmatory tool for detection of the use of synthetic steroids in competitive sport. We review here principles and practices for data processing and calibration of GCC-IRMS data with consideration to anti-doping analyses, with a focus on carbon isotopic analysis (13C/12C). After a brief review of peak definition, the isotopologue signal reduction methods of summation, curve-fitting, and linear regression are described and reviewed. Principles for isotopic calibration are considered in the context of the ?13C = ?13CM – ?13CE difference measurements required for establishing adverse analytical findings for metabolites relative to endogenous reference compounds. Considerations for the anti-doping analyst are reviewed. PMID:22362612

  10. Application of Uranium Isotope Dilution Mass Spectrometry in the preparation of New Certified Reference Materials

    NASA Astrophysics Data System (ADS)

    Hasözbek, A.; Mathew, K. J.; Orlowicz, G.; Srinivasan, B.; Narayanan, U.

    2012-04-01

    Proven measurement techniques play a critical role in the preparation of Certified Reference Materials (CRMs) - those requiring high accuracy and precision in the measurement results. Isotope Dilution Mass Spectrometry (IDMS) is one such measurement method commonly used in the quantitative analysis of uranium in nuclear safeguards and isotope geology applications. In this project, we evaluated the possibility of using some of the uranium isotopic and assay CRMs made earlier by the New Brunswick laboratory as IDMS spikes to define the uranium mass fraction in future preparations of CRMs. Uranium solutions prepared from CRM 112-A (a highly pure uranium metal assay standard) and CRM 115 (a highly pure uranium oxide isotopic and assay standard) were used as spikes in the determination of uranium. Two different thermal ionization mass spectrometer instruments (MAT 261 and TRITON) were used for the isotopic measurements. Standard IDMS equation was used for data reduction to yield results for uranium mass fraction along with uncertainties, the latter calculated according to GUM. The results show that uranium mass fraction measurements can be made with the required accuracy and precision for defining the uranium concentration in new CRMs as well as in routine samples analyses.

  11. Multi-isotope imaging mass spectrometry quantifies stem cell division and metabolism.

    PubMed

    Steinhauser, Matthew L; Bailey, Andrew P; Senyo, Samuel E; Guillermier, Christelle; Perlstein, Todd S; Gould, Alex P; Lee, Richard T; Lechene, Claude P

    2012-01-26

    Mass spectrometry with stable isotope labels has been seminal in discovering the dynamic state of living matter, but is limited to bulk tissues or cells. We developed multi-isotope imaging mass spectrometry (MIMS) that allowed us to view and measure stable isotope incorporation with submicrometre resolution. Here we apply MIMS to diverse organisms, including Drosophila, mice and humans. We test the 'immortal strand hypothesis', which predicts that during asymmetric stem cell division chromosomes containing older template DNA are segregated to the daughter destined to remain a stem cell, thus insuring lifetime genetic stability. After labelling mice with (15)N-thymidine from gestation until post-natal week 8, we find no (15)N label retention by dividing small intestinal crypt cells after a four-week chase. In adult mice administered (15)N-thymidine pulse-chase, we find that proliferating crypt cells dilute the (15)N label, consistent with random strand segregation. We demonstrate the broad utility of MIMS with proof-of-principle studies of lipid turnover in Drosophila and translation to the human haematopoietic system. These studies show that MIMS provides high-resolution quantification of stable isotope labels that cannot be obtained using other techniques and that is broadly applicable to biological and medical research. PMID:22246326

  12. Applications of Structural Mass Spectrometry to Metabolomics: Clarifying Bond Specific Spectral Signatures with Isotope Edited Spectroscopy

    NASA Astrophysics Data System (ADS)

    Gorlova, Olga; Wolke, Conrad T.; Fournier, Joseph; Colvin, Sean; Johnson, Mark; Miller, Scott

    2015-06-01

    Comprehensive FTIR, MS/MS and NMR of pharmaceuticals are generally readily available but characterization of their metabolites has been an obstacle. Atorvastatin is a statin drug responsible for the maintenance of cholesterol in the body. Diovan is an angiostensin receptor antagonist used to treat high blood pressure and congestive heart failure. The field of metabolomics, however, is struggling to obtain the identity of their structures. We implement mass spectrometry with cryogenic ion spectroscopy to study gaseous ions of the desired metabolites which, in combination, not only identify the mass of the metabolite but also elucidate their structures through isotope-specific infrared spectroscopy.

  13. High-resolution quantitative imaging of mammalian and bacterial cells using stable isotope mass spectrometry

    PubMed Central

    Lechene, Claude; Hillion, Francois; McMahon, Greg; Benson, Douglas; Kleinfeld, Alan M; Kampf, J Patrick; Distel, Daniel; Luyten, Yvette; Bonventre, Joseph; Hentschel, Dirk; Park, Kwon Moo; Ito, Susumu; Schwartz, Martin; Benichou, Gilles; Slodzian, Georges

    2006-01-01

    Background Secondary-ion mass spectrometry (SIMS) is an important tool for investigating isotopic composition in the chemical and materials sciences, but its use in biology has been limited by technical considerations. Multi-isotope imaging mass spectrometry (MIMS), which combines a new generation of SIMS instrument with sophisticated ion optics, labeling with stable isotopes, and quantitative image-analysis software, was developed to study biological materials. Results The new instrument allows the production of mass images of high lateral resolution (down to 33 nm), as well as the counting or imaging of several isotopes simultaneously. As MIMS can distinguish between ions of very similar mass, such as 12C15N- and 13C14N-, it enables the precise and reproducible measurement of isotope ratios, and thus of the levels of enrichment in specific isotopic labels, within volumes of less than a cubic micrometer. The sensitivity of MIMS is at least 1,000 times that of 14C autoradiography. The depth resolution can be smaller than 1 nm because only a few atomic layers are needed to create an atomic mass image. We illustrate the use of MIMS to image unlabeled mammalian cultured cells and tissue sections; to analyze fatty-acid transport in adipocyte lipid droplets using 13C-oleic acid; to examine nitrogen fixation in bacteria using 15N gaseous nitrogen; to measure levels of protein renewal in the cochlea and in post-ischemic kidney cells using 15N-leucine; to study DNA and RNA co-distribution and uridine incorporation in the nucleolus using 15N-uridine and 81Br of bromodeoxyuridine or 14C-thymidine; to reveal domains in cultured endothelial cells using the native isotopes 12C, 16O, 14N and 31P; and to track a few 15N-labeled donor spleen cells in the lymph nodes of the host mouse. Conclusion MIMS makes it possible for the first time to both image and quantify molecules labeled with stable or radioactive isotopes within subcellular compartments. PMID:17010211

  14. Quantitation of vitamin B6 in biological samples by isotope dilution mass spectrometry

    SciTech Connect

    Hachey, D.L.; Coburn, S.P.; Brown, L.T.; Erbelding, W.F.; DeMark, B.; Klein, P.D.

    1985-11-15

    Methods have been developed for the simultaneous quantitative analysis of vitamin B6 forms in biological samples by isotope dilution mass spectrometry using deuterated forms of pyridoxine, pyridoxal, pyridoxamine, and pyridoxic acid. The biological fluid or tissue sample was homogenized and then treated with a cocktail containing appropriate amounts of each deuterated vitamer, as well as the deuterated, phosphorylated vitamer forms. The individual vitamers were isolated from the homogenate by a complex high-performance liquid chromatographic procedure that provided separate fractions for each of the six vitamers found in biological samples. Aldehydic B6 vitamers were reduced to the alcohol form prior to acetylation and analysis by gas chromatography/mass spectrometry (GC/MS). The three resulting vitamers were analyzed by electron ionization GC/MS using a silicone capillary column. The methods have been applied to analysis of vitamin B6 in liver, milk, urine, and feces at levels as low as 0.02 nmol/ml.

  15. Stable isotope ratio mass spectrometry of nanogram quantities of boron and sulfur

    NASA Astrophysics Data System (ADS)

    Wieser, Michael Eugene

    1998-09-01

    Instrumentation and analytical techniques were developed to measure isotope abundances from nanograms of sulfur and boron. Sulfur isotope compositions were determined employing continuous flow isotope ratio mass spectroscopy (CF-IRMS) procedures and AsS+ thermal ionization mass spectrometry techniques (AsS+-TIMS). Boron isotope abundances were determined by BO2/sp--TIMS. CF-IRMS measurements realized ?34S values from 10 ?g sulfur with precisions of ±0.3/perthous. To extend sulfur isotope measurements to much smaller samples, a TIMS procedure was developed to measure 75As32S+ and 75As34S+ at masses 108 and 109 from 200 ng S on a Finnigan MAT 262 with an ion counter. This is possibly the smallest amount of sulfur which has been successfully analyzed isotopically. The internal precision of 32S/34S ratios measured by AsS+-TIMS was better than ±0.15 percent. ?34S-values calculated relative to the measured 32S/34S value of an IAEA AG2S standard (S-1) agreed with those determined by CF-IRMS to within ±3/perthous. The increasing sensitivity of S-isotope analyses permits hiterto impossible investigations e.g. sulfur in tree rings and ice cores. Boron isotope abundances were measured as BO2/sp- from 50 ng B using an older thermal ionization mass spectrometer which had been extensively upgraded including the addition of computer control electronics, sensitive ion current amplification and fiber optic data bus. The internal precisions of the measured 11B/10B ratios were ±0.15 percent and the precisions of ?11B values calculated relative to the accepted international standard (SRM-951) were ±3/perthous. Two applications of boron isotope abundance variations were initiated (1) ground waters of Northern Alberta and (2) coffee beans in different regions of the world. In the first it was demonstrated that boron isotopes could be used to trace boron released during steam injection of oil sands into the surrounding environment. Data from the second study suggest that boron isotopes can be used to improve cultivation of coffee particularly in regions where 'organically grown' coffee had markedly different ?11B values than beans grown with boron- containing fertilizers in neighbouring regions. A regional dependence on the ?11B values of the coffee allow the sources of commercial coffee blends to be identified.

  16. A gas chromatography/pyrolysis/isotope ratio mass spectrometry system for high-precision dD measurements

    E-print Network

    Fischer, Hubertus

    A gas chromatography/pyrolysis/isotope ratio mass spectrometry system for high-precision d we present a highly automated, high-precision online gas chromatography/pyrolysis/isotope ratio from ice, preconcentration, gas chromatographic separation and pyrolysis of CH4 from roughly 500 g

  17. Inductively coupled plasma mass spectrometry for stable isotope metabolic tracer studies of living systems

    SciTech Connect

    Luong, E.

    1999-05-10

    This dissertation focuses on the development of methods for stable isotope metabolic tracer studies in living systems using inductively coupled plasma single and dual quadrupole mass spectrometers. Sub-nanogram per gram levels of molybdenum (Mo) from human blood plasma are isolated by the use of anion exchange alumina microcolumns. Million-fold more concentrated spectral and matrix interferences such as sodium, chloride, sulfate, phosphate, etc. in the blood constituents are removed from the analyte. The recovery of Mo from the alumina column is 82 {+-} 5% (n = 5). Isotope dilution inductively coupled plasma mass spectrometry (ID-ICP-MS) is utilized for the quantitative ultra-trace concentration determination of Mo in bovine and human blood samples. The average Mo concentration in reference bovine serum determined by this method is 10.2 {+-} 0.4 ng/g, while the certified value is 11.5 {+-} 1.1 ng/g (95% confidence interval). The Mo concentration of one pool of human blood plasma from two healthy male donors is 0.5 {+-} 0.1 ng/g. The inductively coupled plasma twin quadrupole mass spectrometer (ICP-TQMS) is used to measure the carbon isotope ratio from non-volatile organic compounds and bio-organic molecules to assess the ability as an alternative analytical method to gas chromatography combustion isotope ratio mass spectrometry (GC-combustion-IRMS). Trytophan, myoglobin, and {beta}-cyclodextrin are chosen for the study, initial observation of spectral interference of {sup 13}C{sup +} with {sup 12}C{sup 1}H{sup +} comes from the incomplete dissociation of myoglobin and/or {beta}-cyclodextrin.

  18. Analytical Validation of Accelerator Mass Spectrometry for Pharmaceutical Development: the Measurement of Carbon-14 Isotope Ratio.

    SciTech Connect

    Keck, B D; Ognibene, T; Vogel, J S

    2010-02-05

    Accelerator mass spectrometry (AMS) is an isotope based measurement technology that utilizes carbon-14 labeled compounds in the pharmaceutical development process to measure compounds at very low concentrations, empowers microdosing as an investigational tool, and extends the utility of {sup 14}C labeled compounds to dramatically lower levels. It is a form of isotope ratio mass spectrometry that can provide either measurements of total compound equivalents or, when coupled to separation technology such as chromatography, quantitation of specific compounds. The properties of AMS as a measurement technique are investigated here, and the parameters of method validation are shown. AMS, independent of any separation technique to which it may be coupled, is shown to be accurate, linear, precise, and robust. As the sensitivity and universality of AMS is constantly being explored and expanded, this work underpins many areas of pharmaceutical development including drug metabolism as well as absorption, distribution and excretion of pharmaceutical compounds as a fundamental step in drug development. The validation parameters for pharmaceutical analyses were examined for the accelerator mass spectrometry measurement of {sup 14}C/C ratio, independent of chemical separation procedures. The isotope ratio measurement was specific (owing to the {sup 14}C label), stable across samples storage conditions for at least one year, linear over 4 orders of magnitude with an analytical range from one tenth Modern to at least 2000 Modern (instrument specific). Further, accuracy was excellent between 1 and 3 percent while precision expressed as coefficient of variation is between 1 and 6% determined primarily by radiocarbon content and the time spent analyzing a sample. Sensitivity, expressed as LOD and LLOQ was 1 and 10 attomoles of carbon-14 (which can be expressed as compound equivalents) and for a typical small molecule labeled at 10% incorporated with {sup 14}C corresponds to 30 fg equivalents. AMS provides an sensitive, accurate and precise method of measuring drug compounds in biological matrices.

  19. 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 specific isotope system, it should be noted that the same methods can be used to evaluate any isotope system of interest. ?? 2008 Elsevier B.V.

  20. Isolation of Pu-isotopes from environmental samples using ion chromatography for accelerator mass spectrometry and alpha spectrometry.

    PubMed

    Chamizo, E; Jiménez-Ramos, M C; Wacker, L; Vioque, I; Calleja, A; García-León, M; García-Tenorio, R

    2008-01-14

    A radiochemical method for the isolation of plutonium-isotopes from environmental samples, based on the use of specific extraction chromatography resins for actinides (TEVA), Eichrom Industries, Inc.), has been set up in our laboratory and optimised for their posterior determination by alpha spectrometry (AS) or accelerator mass spectrometry (AMS). The proposed radiochemical method has replaced in our lab a well-established one based on the use of a relatively un-specific anion-exchange resin (AG) 1X8, Bio-rad Laboratories, Inc.), because it is clearly less time consuming, reduces the amounts and molarities of acid wastes produced, and reproducibly gives high radiochemical yields. In order to check the reliability of the proposed radiochemical method for the determination of plutonium-isotopes in different environmental matrixes, twin aliquots of a set of samples were prepared with TEVA and with AG 1X8 resins and measured by AS. Some samples prepared with TEVA resins were measured as well by AMS. As it is shown in the text, there is a comfortable agreement between AS and AMS, which adequately validates the method. PMID:18082656

  1. Nitrogen isotopic analyses by isotope-ratio-monitoring gas chromatography/mass spectrometry

    NASA Technical Reports Server (NTRS)

    Merritt, D. A.; Hayes, J. M.

    1994-01-01

    Amino acids containing natural-abundance levels of 15N were derivatized and analyzed isotopically using a technique in which individual compounds are separated by gas chromatography, combusted on-line, and the product stream sent directly to an isotope-ratio mass spectrometer. For samples of N2 gas, standard deviations of ratio measurement were better than 0.1% (Units for delta are parts per thousand or per million (%).) for samples larger than 400 pmol and better than 0.5% for samples larger than 25 pmol (0.1% 15N is equivalent to 0.00004 atom % 15N). Results duplicated those of conventional, batchwise analyses to within 0.05%. For combustion of organic compounds yielding CO2/N2 ratios between 14 and 28, in particular for N-acetyl n-propyl derivatives of amino acids, delta values were within 0.25% of results obtained using conventional techniques and standard deviations were better than 0.35%. Pooled data for measurements of all amino acids produced an accuracy and precision of 0.04 and 0.23%, respectively, when 2 nmol of each amino acid was injected on column and 20% of the stream of combustion products was delivered to the mass spectrometer.

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

    PubMed

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

    2015-12-01

    A critical component of the biogeochemical cycle of mercury (Hg) is the transformation of inorganic Hg to neurotoxic monomethylmercury (CH3Hg). Humans are exposed to CH3Hg by consuming marine fish, yet the origin of CH3Hg in fish is a topic of debate. The carbon stable isotopic composition (?(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 ?(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 ?(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 ?(13)CCH3Hg values on natural biological samples was performed by combining a CH3Hg selective extraction, purification, and halogenation followed by GC-C-IRMS analysis. Reference ?(13)C values were established for a tuna fish certified material (ERM-CE464) originating from the Adriatic Sea (?(13)CCH3Hg = -22.1 ± 1.5‰, ± 2 SD). This value is similar to the ?(13)C value of marine algal-derived particulate organic carbon (?(13)CPOC = -21‰). PMID:26511394

  3. 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.

  4. Using theoretical protein isotopic distributions to parse small-mass-difference post-translational interactions via mass spectrometry

    PubMed Central

    Rhoads, Timothy W.; Williams, Jared R.; Lopez, Nathan I.; Morré, Jeffrey T.; Bradford, C. Samuel; Beckman, Joseph S.

    2014-01-01

    Small-mass-difference modifications to proteins are obscured in mass spectrometry by the natural abundance of stable isotopes such as 13C that broaden the isotopic distribution of an intact protein. Using a ZipTip™ to remove salt from proteins in preparation for high-resolution mass spectrometry, the theoretical isotopic distribution intensities calculated from the protein’s empirical formula could be fit to experimentally acquired data and used to differentiate between multiple low-mass modifications to proteins. We could readily distinguish copper from zinc bound to a single-metal superoxide dismutase (SOD1) species; copper and zinc only differ by an average mass of 1.8 Daltons and have overlapping stable isotope patterns. In addition, proteins could be directly modified while bound to the ZipTip. For example, washing 11 mM S-methyl methanethiosulfonate over the ZipTip allowed the number of free cysteines on proteins to be detected as S-methyl adducts. Alternatively, washing with the sulfhydryl oxidant diamide could quickly reestablish disulfide bridges. Using these methods, we could resolve the relative contributions of copper and zinc binding, as well as disulfide reduction to intact SOD1 protein present from <100 µg of the lumbar spinal cord of a transgenic, SOD1 overexpressing mouse. Although techniques like ICP-MS can measure total metal in solution, this is the first method able to assess the metal-binding and sulfhydryl reduction of SOD1 at the individual subunit level and is applicable to many other proteins. PMID:23247967

  5. Using Theoretical Protein Isotopic Distributions to Parse Small-Mass-Difference Post-Translational Modifications via Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Rhoads, Timothy W.; Williams, Jared R.; Lopez, Nathan I.; Morré, Jeffrey T.; Bradford, C. Samuel; Beckman, Joseph S.

    2013-01-01

    Small-mass-difference modifications to proteins are obscured in mass spectrometry by the natural abundance of stable isotopes such as 13C that broaden the isotopic distribution of an intact protein. Using a ZipTip (Millipore, Billerica, MA, USA) to remove salt from proteins in preparation for high-resolution mass spectrometry, the theoretical isotopic distribution intensities calculated from the protein's empirical formula could be fit to experimentally acquired data and used to differentiate between multiple low-mass modifications to proteins. We could readily distinguish copper from zinc bound to a single-metal superoxide dismutase (SOD1) species; copper and zinc only differ by an average mass of 1.8 Da and have overlapping stable isotope patterns. In addition, proteins could be directly modified while bound to the ZipTip. For example, washing 11 mM S-methyl methanethiosulfonate over the ZipTip allowed the number of free cysteines on proteins to be detected as S-methyl adducts. Alternatively, washing with the sulfhydryl oxidant diamide could quickly reestablish disulfide bridges. Using these methods, we could resolve the relative contributions of copper and zinc binding, as well as disulfide reduction to intact SOD1 protein present from <100 ?g of the lumbar spinal cord of a transgenic, SOD1 overexpressing mouse. Although techniques like ICP-MS can measure total metal in solution, this is the first method able to assess the metal-binding and sulfhydryl reduction of SOD1 at the individual subunit level and is applicable to many other proteins.

  6. Stable isotope labeling strategy for curcumin metabolite study in human liver microsomes by liquid chromatography-tandem mass spectrometry.

    PubMed

    Gao, Dan; Chen, Xiaowu; Yang, Xiaomei; Wu, Qin; Jin, Feng; Wen, Hongliang; Jiang, Yuyang; Liu, Hongxia

    2015-04-01

    The identification of drug metabolites is very important in drug development. Nowadays, the most widely used methods are isotopes and mass spectrometry. However, the commercial isotopic labeled reagents are usually very expensive, and the rapid and convenient identification of metabolites is still difficult. In this paper, an (18)O isotope labeling strategy was developed and the isotopes were used as a tool to identify drug metabolites using mass spectrometry. Curcumin was selected as a model drug to evaluate the established method, and the (18)O labeled curcumin was successfully synthesized. The non-labeled and (18)O labeled curcumin were simultaneously metabolized in human liver microsomes (HLMs) and analyzed by liquid chromatography/mass spectrometry (LC-MS). The two groups of chromatograms obtained from metabolic reaction mixture with and without cofactors were compared and analyzed using Metabolynx software (Waters Corp., Milford, MA, USA). The mass spectra of the newly appearing chromatographic peaks in the experimental sample were further analyzed to find the metabolite candidates. Their chemical structures were confirmed by tandem mass spectrometry. Three metabolites, including two reduction products and a glucuronide conjugate, were successfully detected under their specific HLMs metabolic conditions, which were in accordance with the literature reported results. The results demonstrated that the developed isotope labeling method, together with post-acquisition data processing using Metabolynx software, could be used for fast identification of new drug metabolites. PMID:25592681

  7. Stable Isotope Labeling Strategy for Curcumin Metabolite Study in Human Liver Microsomes by Liquid Chromatography-Tandem Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Gao, Dan; Chen, Xiaowu; Yang, Xiaomei; Wu, Qin; Jin, Feng; Wen, Hongliang; Jiang, Yuyang; Liu, Hongxia

    2015-04-01

    The identification of drug metabolites is very important in drug development. Nowadays, the most widely used methods are isotopes and mass spectrometry. However, the commercial isotopic labeled reagents are usually very expensive, and the rapid and convenient identification of metabolites is still difficult. In this paper, an 18O isotope labeling strategy was developed and the isotopes were used as a tool to identify drug metabolites using mass spectrometry. Curcumin was selected as a model drug to evaluate the established method, and the 18O labeled curcumin was successfully synthesized. The non-labeled and 18O labeled curcumin were simultaneously metabolized in human liver microsomes (HLMs) and analyzed by liquid chromatography/mass spectrometry (LC-MS). The two groups of chromatograms obtained from metabolic reaction mixture with and without cofactors were compared and analyzed using Metabolynx software (Waters Corp., Milford, MA, USA). The mass spectra of the newly appearing chromatographic peaks in the experimental sample were further analyzed to find the metabolite candidates. Their chemical structures were confirmed by tandem mass spectrometry. Three metabolites, including two reduction products and a glucuronide conjugate, were successfully detected under their specific HLMs metabolic conditions, which were in accordance with the literature reported results. The results demonstrated that the developed isotope labeling method, together with post-acquisition data processing using Metabolynx software, could be used for fast identification of new drug metabolites.

  8. Quantification of monofluoroacetate and monochloroacetate in human urine by isotope dilution liquid chromatography tandem mass spectrometry.

    PubMed

    Hamelin, Elizabeth I; Mawhinney, Douglas B; Parry, Ritchard; Kobelski, Robert J

    2010-05-01

    The rodenticide monofluoroacetate (MFA) and monochloroacetate (MCA), a chemical intermediate from several chemical syntheses, have been identified as potential agents of chemical terrorism due to their high toxicity. In preparation for response to poisonings and mass exposures, we have developed a quantification method using isotopic dilution to determine MFA and MCA in urine from 50 to 5000 ng/mL. Both analytes were extracted from urine using solid-phase extraction; extraction recoveries were 62% (MFA) and 76% (MCA). The extracts were then separated with isocratic high-performance liquid chromatography and identified using electrospray ionization tandem mass spectrometry, with detection limits of 0.9 and 7.0 ng/mL for MFA and MCA, respectively. Selectivity was established for both analytes with unique chromatographic retention times which were correlated with isotopically labeled internal standards and the use of two mass spectral transitions for each compound. The intra-day variability was less than 5% for both analytes and the inter-day variability was 7% for MFA and 6% for MCA. PMID:20356806

  9. 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.

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

    NASA Astrophysics Data System (ADS)

    Giebel, Brian M.

    2011-12-01

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

  11. Daily cortisol production rate in man determined by stable isotope dilution/mass spectrometry

    SciTech Connect

    Esteban, N.V.; Loughlin, T.; Yergey, A.L.; Zawadzki, J.K.; Booth, J.D.; Winterer, J.C.; Loriaux, D.L. )

    1991-01-01

    Growth retardation as well as the development of Cushingoid features in adrenally insufficient patients treated with the currently accepted replacement dose of cortisol (33-41 mumol/day.m2; 12-15 mg/m2.day) prompted us to reevaluate the cortisol production rate (FPR) in normal subjects and patients with Cushing's syndrome, using a recently developed thermospray liquid chromatography-mass spectrometry method. The stable isotope (9,12,12-2H3)cortisol was infused continuously for 31 h at about 5% of the anticipated FPR. Blood samples were obtained at 20-min intervals for 24 h, spun, and pooled in 4-h groups. Tracer dilution in plasma was determined by liquid chromatography/mass spectrometry. The method was validated with controlled infusions in 6 patients with adrenal insufficiency. Results from 12 normal volunteers revealed a FPR of 27.3 +/- 7.5 mumol/day (9.9 +/- 2.7 mg/day) or 15.7 mumol/day.m2; 5.7 mg/m2. day. A previously unreported circadian variation in FPR was observed. Patients with Cushing's syndrome demonstrated unequivocal elevation of FPR and cortisol concentration correlated during each sample period in normal volunteers, indicating that cortisol secretion, rather than metabolism, is mainly responsible for changes in plasma cortisol. Our data suggest that the FPR in normal subjects may be lower than previously believed.

  12. Sulfur-based absolute quantification of proteins using isotope dilution inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Lee, Hyun-Seok; Heun Kim, Sook; Jeong, Ji-Seon; Lee, Yong-Moon; Yim, Yong-Hyeon

    2015-10-01

    An element-based reductive approach provides an effective means of realizing International System of Units (SI) traceability for high-purity biological standards. Here, we develop an absolute protein quantification method using double isotope dilution (ID) inductively coupled plasma mass spectrometry (ICP-MS) combined with microwave-assisted acid digestion for the first time. We validated the method and applied it to certify the candidate protein certified reference material (CRM) of human growth hormone (hGH). The concentration of hGH was determined by analysing the total amount of sulfur in hGH. Next, the size-exclusion chromatography method was used with ICP-MS to characterize and quantify sulfur-containing impurities. By subtracting the contribution of sulfur-containing impurities from the total sulfur content in the hGH CRM, we obtained a SI-traceable certification value. The quantification result obtained with the present method based on sulfur analysis was in excellent agreement with the result determined via a well-established protein quantification method based on amino acid analysis using conventional acid hydrolysis combined with an ID liquid chromatography-tandem mass spectrometry. The element-based protein quantification method developed here can be generally used for SI-traceable absolute quantification of proteins, especially pure-protein standards.

  13. Determination of iodine in oyster tissue by isotope dilution laser resonance ionization mass spectrometry

    SciTech Connect

    Fassett, J.D.; Murphy, T.J. )

    1990-02-15

    The technique of laser resonance ionization mass spectrometry has been combined with isotope dilution analysis to determine iodine in oyster tissue. The long-lived radioisotope, 129I, was used to spike the samples. Samples were equilibrated with the 129I, wet ashed under controlled conditions, and iodine separated by coprecipitation with silver chloride. The analyte was dried as silver ammonium iodide upon a tantalum filament from which iodine was thermally desorbed in the resonance ionization mass spectrometry instrument. A single-color, two-photon resonant plus one-photon ionization scheme was used to form positive iodine ions. Long-lived iodine signals were achieved from 100 ng of iodine. The precision of 127I/129I measurement has been evaluated by replicate determinations of the spike, the spike calibration samples, and the oyster tissue samples and was 1.0%. Measurement precision among samples was 1.9% for the spike calibration and 1.4% for the oyster tissue. The concentration of iodine determined in SRM 1566a, Oyster Tissue, was 4.44 micrograms/g with an estimate of the overall uncertainty for the analysis of +/- 0.12 microgram/g.

  14. Development of melamine certified reference material in milk using two different isotope dilution mass spectrometry techniques.

    PubMed

    Hon, Phoebe Y T; Chu, Patricia W S; Cheng, Chi-ho; Lee, Terry C L; Chan, Pui-kwan; Cheung, Samuel T C; Wong, Yiu-chung

    2011-09-28

    A new certified reference material (CRM) of melamine in milk GLHK-11-02 was developed aiming to address the great demand from the testing community after the melamine crises. The material was prepared by adding an appropriate quantity of melamine into the skimmed milk samples and the final product was in the form of fine lyophilized powder. Characterization of the material relied on two newly developed gravimetric isotope dilution mass spectrometry (IDMS) methods, one using liquid chromatography-tandem mass spectrometry (LC-MS/MS) and another gas chromatography-mass spectrometry (GC-MS). Experimental parameters with crucial effects on the performance of the two IDMS methods were thoroughly investigated. These included purity of standard used, equilibration time of isotopes, efficiency of extraction methods as well as possible interferences from the matrix and melamine analogues. Precision was found to be excellent with a coefficient of variation of 2.5% for the LC-IDMS/MS (n=46) and 1.9% for the GC-IDMS (n=30) respectively. Using one-tail Student's t-test at 95% confidence interval, analytical data sets generated from the two methods were found to exhibit no significant difference. Measurement accuracy of the methods was further verified through an Asia Pacific Metrology Program (APMP) pilot study. Analytical results of the present LC-IDMS/MS for the two milk test samples at the concentration level of about 0.45 and 3.5 mg kg(-1) were proven to be very good. There were excellent overlaps between our results and the assigned reference values, and the absolute deviation was less than 3.2%. Both the LC-IDMS/MS and GC-IDMS methods were shown to be sufficiently reliable and accurate for certification of the melamine CRM. Certified value of melamine in dry mass fraction in GLHK-11-02 was 1.14 mg kg(-1). Expanded uncertainty due to sample inhomogeneity, long term and short term stability and variability in the characterization procedure was at 7.1% or 0.08 mg kg(-1). The CRM is primarily used to provide a complete method validation for and to improve the technical competence of melamine analysis to food and chemical testing laboratories. PMID:21872867

  15. Quantification of ferritin bound iron in human serum using species-specific isotope dilution mass spectrometry.

    PubMed

    Ren, Yao; Walczyk, Thomas

    2014-09-01

    Ferritin is a hollow sphere protein composed of 24 subunits that can store up to 4500 iron atoms in its inner cavity. It is mainly found in the liver and spleen but also in serum at trace levels. Serum ferritin is considered as the best single indicator in assessing body iron stores except liver or bone marrow biopsy. However, it is confounded by other disease conditions. Ferritin bound iron (FBI) and ferritin saturation have been suggested as more robust biomarkers. The current techniques for FBI determination are limited by low antibody specificity, low instrument sensitivity and possible analyte losses during sample preparation. The need for a highly sensitive and reliable method is widely recognized. Here we describe a novel technique to detect serum FBI using species-specific isotope dilution mass spectrometry (SS-IDMS). [(57)Fe]-ferritin was produced by biosynthesis and in vitro labeling with the (57)Fe spike in the form of [(57)Fe]-citrate after cell lysis and heat treatment. [(57)Fe]-ferritin for sample spiking was further purified by fast liquid protein chromatography. Serum ferritin and added [(57)Fe]-ferritin were separated from other iron species by ultrafiltration followed by isotopic analysis of FBI using negative thermal ionization mass spectrometry. Repeatability of our assay is 8% with an absolute detection limit of 18 ng FBI in the sample. As compared to other speciation techniques, SS-IDMS offers maximum control over sample losses and species conversion during analysis. The described technique may therefore serve as a reference technique for clinical applications of FBI as a new biomarker for assessing body iron status. PMID:25008269

  16. Biomedical applications of accelerator mass spectrometry-isotope measurements at the level of the atom.

    PubMed

    Barker, J; Garner, R C

    1999-01-01

    Accelerator mass spectrometry (AMS) is a nuclear physics technique developed about twenty years ago, that uses the high energy (several MeV) of a tandem Van de Graaff accelerator to measure very small quantities of rare and long-lived isotopes. Elements that are of interest in biomedicine and environmental sciences can be measured, often to parts per quadrillion sensitivity, i.e. zeptomole to attomole levels (10(-21)-10(-18) mole) from milligram samples. This is several orders of magnitude lower than that achievable by conventional decay counting techniques, such as liquid scintillation counting (LSC). AMS was first applied to geochemical, climatological and archaeological areas, such as for radiocarbon dating (Shroud of Turin), but more recently this technology has been used for bioanalytical applications. In this sphere, most work has been conducted using aluminium, calcium and carbon isotopes. The latter is of special interest in drug metabolism studies, where a Phase 1 adsorption, distribution, metabolism and excretion (ADME) study can be conducted using only 10 nanoCurie (37 Bq or ca. 0.9 microSv) amounts or less of 14C-labelled drugs. In the UK, these amounts of radioactivity are below those necessary to request specific regulatory approval from the Department of Health's Administration of Radioactive Substances Advisory Committee (ARSAC), thus saving on valuable development time and resources. In addition, the disposal of these amounts is much less an environmental issue than that associated with microCurie quantities, which are currently used. Also, AMS should bring an opportunity to conduct "first into man" studies without the need for widespread use of animals. Centre for Biomedical Accelerator Mass Spectrometry (CBAMS) Ltd. is the first fully commercial company in the world to offer analytical services using AMS. With its high throughput and relatively low costs per sample analysis, AMS should be of great benefit to the pharmaceutical and biotechnology industries as well as other life science areas. PMID:10097404

  17. The Determination of the Natural Abundance of the Isotopes of Chlorine: An Introductory Experiment in Mass Spectrometry.

    ERIC Educational Resources Information Center

    O'Malley, Rebecca M.

    1982-01-01

    Describes a laboratory experiment which introduces basic principles and experimental techniques of mass spectrometry for fourth year undergraduate (B.Sc.) students. Laboratory procedures, background information, and discussion of results are provided for the experiment in which the natural isotopic abundance of chlorine is determined. (Author/JN)

  18. Split-Field Drift Tube/Mass Spectrometry and Isotopic Labeling Techniques for Determination of Single Amino Acid Polymorphisms

    E-print Network

    Clemmer, David E.

    of Single Amino Acid Polymorphisms Stephen J. Valentine, S. Sevugarajan, Ruwan T. Kurulugama, Stormy L/mass spectrometry and isotopic labeling techniques is evaluated as a means of identifying single amino acid, these species have identical mobility distributions. Peptides having sequences that differ by one amino acid

  19. Spatially tracking 13C labeled substrate (bicarbonate) accumulation in microbial communities using laser ablation isotope ratio mass spectrometry

    SciTech Connect

    Moran, James J.; Doll, Charles G.; Bernstein, Hans C.; Renslow, Ryan S.; Cory, Alexandra B.; Hutchison, Janine R.; Lindemann, Stephen R.; Fredrickson, Jim K.

    2014-08-25

    This is a manuscript we would like to submit for publication in Environmental Microbiology Reports. This manuscript contains a description of a laser ablation isotope ratio mass spectrometry methodology developed at PNNL and applied to a microbial system at a PNNL project location – Hot Lake, Washington. I will submit a word document containing the entire manuscript with this Erica input request form.

  20. Forensic Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Hoffmann, William D.; Jackson, Glen P.

    2015-07-01

    Developments in forensic mass spectrometry tend to follow, rather than lead, the developments in other disciplines. Examples of techniques having forensic potential born independently of forensic applications include ambient ionization, imaging mass spectrometry, isotope ratio mass spectrometry, portable mass spectrometers, and hyphenated chromatography-mass spectrometry instruments, to name a few. Forensic science has the potential to benefit enormously from developments that are funded by other means, if only the infrastructure and personnel existed to adopt, validate, and implement the new technologies into casework. Perhaps one unique area in which forensic science is at the cutting edge is in the area of chemometrics and the determination of likelihood ratios for the evaluation of the weight of evidence. Such statistical techniques have been developed most extensively for ignitable-liquid residue analyses and isotope ratio analysis. This review attempts to capture the trends, motivating forces, and likely impact of developing areas of forensic mass spectrometry, with the caveat that none of this research is likely to have any real impact in the forensic community unless: (a) The instruments developed are turned into robust black boxes with red and green lights for positives and negatives, respectively, or (b) there are PhD graduates in the workforce who can help adopt these sophisticated techniques.

  1. [Determination of endogenous agmatine in rat plasma by isotope dilution-gas chromatography-mass spectrometry].

    PubMed

    Qiu, Zhongli; Lin, Ying; Xiong, Zhili; Xie, Jianwei

    2014-07-01

    A method for the determination of endogenous agmatine in rat plasma was developed by isotope dilution-gas chromatography-negative chemical ionization mass spectrometry (GC-NCI/MS). The plasma samples were analyzed after protein precipitation, evaporation, derivatization by hexafluoroacetone (HFAA), and clean-up on a Florisil SPE column. The GC-MS analysis utilized stable isotope d8-agmatine as internal standard. The samples after treatme were tested by negative chemical ionization with selected ion monitoring (SIM) which was set at m/z 492 (molecular ion of agmatine) and m/z 500 (molecular ion of internal standard). The limit of detection (LOD) of agmatine standard solution was 0.005 7 ng/mL. The calibration curve of the agmatine spiked in rat plasma showed a good linear relationship at the range of 1.14-57.0 ng/mL (r = 0.997). The recoveries of agmatine spiked in rat plasma ranged from 92.3% to 109.8%. Inter-day and intra-day precisions were less than 15%. The average concentration level of agmatine in rat plasma was (22 +/- 9) ng/mL, and there was no significant difference between male and female SD rats (p > 0.05). The method is high sensitive and specific, and can be used for the determination of endogenous agmatine in plasma. It provides a strong support for the subsequent research of agmatine. PMID:25255573

  2. 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

  3. Development of hemoglobin A1c certified reference material by liquid chromatography isotope dilution mass spectrometry.

    PubMed

    Bi, Jiaming; Wu, Liqing; Yang, Bin; Yang, Yi; Wang, Jing

    2012-04-01

    We report the development of a National Institute of Metrology (NIM) hemoglobin A(1c) (HbA(1c)) certified reference material (CRM). Each CRM unit contains about 10 ?L of hemoglobin. Both hemoglobin and glycated hemoglobin were quantitatively determined by high-performance liquid chromatography (HPLC)-isotope dilution mass spectrometry (IDMS) with synthesized VHLTPE and glycated VHLTPE as standards. The mass fraction of synthesized VHLTPE or glycated VHLTPE was also quantitatively determined by HPLC-IDMS with NIM amino acid CRMs as standards. The homogeneity and stability of the CRMs were examined with a commercial HbA(1c) analyzer based on the HPLC principle. Fifteen units were randomly selected for homogeneity examination, and statistical analysis showed there was no inhomogeneity. Examination of the stability showed that the CRM was stable for at least 6 months at -80 °C. Uncertainty components of the balance, amino acid purity, hydrolysis and proteolysis efficiency, method reproducibility, homogeneity, and stability were taken into consideration for uncertainty evaluation. The certified value of NIM HbA(1c) CRM was expressed as the ratio of HbA(1c) to total hemoglobin in moles, and was (9.6 ± 1.9)%. The CRM can be used as a calibration or validation standard for clinical diagnostics. It is expected to improve the comparability for HbA(1c) measurement in China. PMID:22349405

  4. Investigation of bn-44 peptide fragments using high resolution mass spectrometry and isotope labeling.

    PubMed

    Wang, Bing; Yu, Jiayi; Wang, Huixin; Wei, Zhonglin; Guo, Xinhua; Xiao, Zhaohui; Zeng, Zhoufang; Kong, Wei

    2014-12-01

    An N-terminal deuterohemin-containing hexapeptide (DhHP-6) was designed as a short peptide cytochrome c (Cyt c) mimetic to study the effect of N-terminal charge on peptide fragmentation pathways. This peptide gave different dissociation patterns than normal tryptic peptides. Upon collision-induced dissociation (CID) with an ion trap mass spectrometer, the singly charged peptide ion containing no added proton generated abundant and characteristic bn-44 ions instead of bn-28 (an) ions. Studies by high resolution mass spectrometry (HRMS) and isotope labeling indicate that elimination of 44 Da fragments from b ions occurs via two different pathways: (1) loss of CH3CHO (44.0262) from a Thr side chain; (2) loss of CO2 (43.9898) from the oxazolone structure in the C-terminus. A series of analogues were designed and analyzed. The experimental results combined with Density Functional Theory (DFT) calculations on the proton affinity of the deuteroporphyrin demonstrate that the production of these novel bn-44 ions is related to the N-terminal charge via a charge-remote rather than radical-directed fragmentation pathway. PMID:25280401

  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. Isotope-ratio-monitoring gas chromatography-mass spectrometry: methods for isotopic calibration

    NASA Technical Reports Server (NTRS)

    Merritt, D. A.; Brand, W. A.; Hayes, J. M.

    1994-01-01

    In trial analyses of a series of n-alkanes, precise determinations of 13C contents were based on isotopic standards introduced by five different techniques and results were compared. Specifically, organic-compound standards were coinjected with the analytes and carried through chromatography and combustion with them; or CO2 was supplied from a conventional inlet and mixed with the analyte in the ion source, or CO2 was supplied from an auxiliary mixing volume and transmitted to the source without interruption of the analyte stream. Additionally, two techniques were investigated in which the analyte stream was diverted and CO2 standards were placed on a near-zero background. All methods provided accurate results. Where applicable, methods not involving interruption of the analyte stream provided the highest performance (sigma = 0.00006 at.% 13C or 0.06% for 250 pmol C as CO2 reaching the ion source), but great care was required. Techniques involving diversion of the analyte stream were immune to interference from coeluting sample components and still provided high precision (0.0001 < or = sigma < or = 0.0002 at.% or 0.1 < or = sigma < or = 0.2%).

  7. Isotope Ratio Mass Spectrometry and Shale Gas - What Is Possible with Current Technology?

    NASA Astrophysics Data System (ADS)

    Barrie, C. D.; Kasson, A.

    2014-12-01

    With ever increasing exploration and exploitation of 'unconventional' hydrocarbon resources, the drive to understand the origins, history and importance of these resources and their effects on the surrounding environment (i.e. ground waters) has never been more important. High-throughput, high-precision isotopic measurements are therefore a key tool in this industry to both understand the gas generated and monitor the development and stability of wells through time. With the advent of cavity ringdown spectroscopy (CRDS) instrumentation, there has been a push in some applications - environmental & atmospheric - to gather more and more data directly at the location of collection or at dedicated field stations. Furthermore, CRDS has resulted in users seeking greater autonomy of instrumentation and so-called black box technology. Traditionally IRMS technology has not met any of these demands, requiring very specific and extensive footprint, power and environmental requirements. This has meant that the 'Oil & Gas' sector, which for natural gases measurements requires GC-IRMS technology - not possible via CRDS - loses time, money and manpower as samples get sent to central facility or contract labs with potentially long lee times. However, recent developments in technology mean that IRMS systems exist which are benchtop, have much lower power requirements, standard power connections and as long as housed in a temperature controlled field stations can be deployed anywhere. Furthermore, with advances in electronics and software IRMS systems are approaching the black box level of newer instrumentation while maintaining the flexibility and abilities of isotope ratio mass spectrometry. This presentation will outline changes in IRMS technology applicable to the Oil & Gas industry, discuss the feasibility of true 'field' deployability and present results from a range of Oil & Gas samples.

  8. Application of isotope dilution mass spectrometry: determination of ochratoxin A in the Canadian Total Diet Study

    PubMed Central

    Tam, J.; Pantazopoulos, P.; Scott, P.M.; Moisey, J.; Dabeka, R.W.; Richard, I.D.K.

    2011-01-01

    Analytical methods are generally developed and optimized for specific commodities. Total Diet Studies, representing typical food products ‘as consumed’, pose an analytical challenge since every food product is different. In order to address this technical challenge, a selective and sensitive analytical method was developed suitable for the quantitation of ochratoxin A (OTA) in Canadian Total Diet Study composites. The method uses an acidified solvent extraction, an immunoaffinity column (IAC) for clean-up, liquid chromatography-tandem mass spectrometry (LC-MS/MS) for identification and quantification, and a uniformly stable isotope-labelled OTA (U-[13C20]-OTA) as an internal recovery standard. Results are corrected for this standard. The method is accurate (101% average recovery) and precise (5.5% relative standard deviation (RSD)) based on 17 duplicate analysis of various food products over 2 years. A total of 140 diet composites were analysed for OTA as part of the Canadian Total Diet Study. Samples were collected at retail level from two Canadian cities, Quebec City and Calgary, in 2008 and 2009, respectively. The results indicate that 73% (102/140) of the samples had detectable levels of OTA, with some of the highest levels of OTA contamination found in the Canadian bread supply. PMID:21623499

  9. Measurement of trimethylamine-N-oxide by stable isotope dilution liquid chromatography tandem mass spectrometry.

    PubMed

    Wang, Zeneng; Levison, Bruce S; Hazen, Jennie E; Donahue, Lillian; Li, Xin-Min; Hazen, Stanley L

    2014-06-15

    Trimethylamine-N-oxide (TMAO) levels in blood predict future risk for major adverse cardiac events including myocardial infarction, stroke, and death. Thus, the rapid determination of circulating TMAO concentration is of clinical interest. Here we report a method to measure TMAO in biological matrices by stable isotope dilution liquid chromatography tandem mass spectrometry (LC/MS/MS) with lower and upper limits of quantification of 0.05 and >200?M, respectively. Spike and recovery studies demonstrate an accuracy at low (0.5?M), mid (5?M), and high (100?M) levels of 98.2, 97.3, and 101.6%, respectively. Additional assay performance metrics include intraday and interday coefficients of variance of <6.4 and <9.9%, respectively, across the range of TMAO levels. Stability studies reveal that TMAO in plasma is stable both during storage at -80°C for 5years and to multiple freeze thaw cycles. Fasting plasma normal range studies among apparently healthy subjects (n=349) show a range of 0.73-126?M, median (interquartile range) levels of 3.45 (2.25-5.79)?M, and increasing values with age. The LC/MS/MS-based assay reported should be of value for further studies evaluating TMAO as a risk marker and for examining the effect of dietary, pharmacologic, and environmental factors on TMAO levels. PMID:24704102

  10. Improvements on high-precision measurement of bromine isotope ratios by multicollector inductively coupled plasma mass spectrometry.

    PubMed

    Wei, Hai-Zhen; Jiang, Shao-Yong; Zhu, Zhi-Yong; Yang, Tao; Yang, Jing-Hong; Yan, Xiong; Wu, He-Pin; Yang, Tang-Li

    2015-10-01

    A new, feasible procedure for high-precision bromine isotope analysis using multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) is described. With a combination of HR mass resolution mode and accurate optimization of the Zoom Optics parameters (Focus Quad: -1.30; Zoom Quad: 0.00), the challenging problem of the isobaric interferences ((40)Ar(38)ArH(+) and (40)Ar(40)ArH(+)) in the measurement of bromine isotopes ((79)Br(+), (81)Br(+)) has been effectively solved. The external reproducibility of the measured (81)Br/(79)Br ratios in the selected standard reference materials ranged from ±0.03‰ to ±0.14‰, which is superior to or equivalent to the best results from previous contributions. The effect of counter cations on the Br(+) signal intensity and the instrumental-induced mass bias was evaluated as the loss of HBr aerosol in nebulizer and potential diffusive isotope fractionations. PMID:26078163

  11. Experimental evaluation of the measurement of isotope ratios by time of flight mass spectrometry with laser ablation

    NASA Astrophysics Data System (ADS)

    Vors, E.; Semerok, A.; Wagner, J.-F.

    Time of flight mass spectrometry (TOF-MS) in combination with laser ablation (LA) applied for low isotope composition measurements is limited by energy and spatial dispersion of ions, spatial charge density, and some other factors. In order to reduce these factors that make the extraction of the plasma ions difficult, we used a second laser to create ions by non-isotope-selective photoionization of neutral particles. The photoionization was carried out in uranium vapor beam by the third harmonic of a pulsed Nd:YAG laser. This work presents the results of tentative experiments to estimate the characteristics of the LA-TOF-MS method with non-selective photoionization.

  12. Discovering Mercury Protein Modifications in Whole Proteomes Using Natural Isotope Distributions Observed in Liquid Chromatography-Tandem Mass Spectrometry

    SciTech Connect

    Polacco, Benjamin J.; Purvine, Samuel O.; Zink, Erika M.; LaVoie, Stephen P.; Lipton, Mary S.; Summers, Anne O.; Miller, Susan M.

    2011-08-01

    The identification of peptides that result from post-translational modifications is critical for understanding normal pathways of cellular regulation as well as identifying damage from, or exposures to xenobiotics, i.e. the exposome. However, because of their low abundance in proteomes, effective detection of modified peptides by mass spectrometry (MS) typically requires enrichment to eliminate false identifications. We present a new method for confidently identifying peptides with mercury (Hg)-containing adducts that is based on the influence of mercury’s seven stable isotopes on peptide isotope distributions detected by high-resolution MS. Using a pure protein and E. coli cultures exposed to phenyl mercuric acetate, we show the pattern of peak heights in isotope distributions from primary MS single scans efficiently identified Hg adducts in data from chromatographic separation coupled with tandem mass spectrometry with sensitivity and specificity greater than 90%. Isotope distributions are independent of peptide identifications based on peptide fragmentation (e.g. by SEQUEST), so both methods can be combined to eliminate false positives. Summing peptide isotope distributions across multiple scans improved specificity to 99.4% and sensitivity above 95%, affording identification of an unexpected Hg modification. We also illustrate the theoretical applicability of the method for detection of several less common elements including the essential element, selenium, as selenocysteine in peptides.

  13. In-Gel Stable-Isotope Labeling (ISIL): a strategy for mass spectrometry-based relative quantification.

    PubMed

    Asara, John M; Zhang, Xiang; Zheng, Bin; Christofk, Heather H; Wu, Ning; Cantley, Lewis C

    2006-01-01

    Most proteomics approaches for relative quantification of protein expression use a combination of stable-isotope labeling and mass spectrometry. Traditionally, researchers have used difference gel electrophoresis (DIGE) from stained 1D and 2D gels for relative quantification. While differences in protein staining intensity can often be visualized, abundant proteins can obscure less abundant proteins, and quantification of post-translational modifications is difficult. A method is presented for quantifying changes in the abundance of a specific protein or changes in specific modifications of a protein using In-gel Stable-Isotope Labeling (ISIL). Proteins extracted from any source (tissue, cell line, immunoprecipitate, etc.), treated under two experimental conditions, are resolved in separate lanes by gel electrophoresis. The regions of interest (visualized by staining) are reacted separately with light versus heavy isotope-labeled reagents, and the gel slices are then mixed and digested with proteases. The resulting peptides are then analyzed by LC-MS to determine relative abundance of light/heavy isotope pairs and analyzed by LC-MS/MS for identification of sequence and modifications. The strategy compares well with other relative quantification strategies, and in silico calculations reveal its effectiveness as a global relative quantification strategy. An advantage of ISIL is that visualization of gel differences can be used as a first quantification step followed by accurate and sensitive protein level stable-isotope labeling and mass spectrometry-based relative quantification. PMID:16396506

  14. Chemical and isotopic measurements of micrometeoroids by secondary ion mass spectrometry (A0187-2)

    NASA Technical Reports Server (NTRS)

    Foote, J. H.; Swan, P. D.; Walker, R. M.; Zinner, E. K.; Bahr, D.; Fechtig, H.; Jessberger, E.; Igenbergs, E.; Kreitmayr, U.; Kuczera, H.

    1984-01-01

    The objective of this experiment is to measure the chemical and isotopic composition of interplanetary dust particles of mass greater than 10 to the minus 10 power G for most of thermator elements expected to be present.

  15. Simultaneous Determination of Selected B Vitamins in the NIST SRM 3280 Multivitamin/Multielement Tablets by Liquid Chromatography Isotope Dilution Mass Spectrometry

    Technology Transfer Automated Retrieval System (TEKTRAN)

    There is increased interest in accurately assessing the total dietary intake of vitamins from all sources, including foods and dietary supplements. Isotope dilution mass spectrometry (IDMS) can be a definitive analytical method for very accurate concentration determinations. A liquid chromatographic...

  16. DETERMINATION OF 237NP AND PU ISOTOPES IN LARGE SOIL SAMPLES BY INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY

    SciTech Connect

    Maxwell, S.

    2010-07-26

    A new method for the determination of {sup 237}Np and Pu isotopes in large soil samples has been developed that provides enhanced uranium removal to facilitate assay by inductively coupled plasma mass spectrometry (ICP-MS). This method allows rapid preconcentration and separation of plutonium and neptunium in large soil samples for the measurement of {sup 237}Np and Pu isotopes by ICP-MS. {sup 238}U can interfere with {sup 239}Pu measurement by ICP-MS as {sup 238}UH{sup +} mass overlap and {sup 237}Np via {sup 238}U peak tailing. The method provides enhanced removal of uranium by separating Pu and Np initially on TEVA Resin, then transferring Pu to DGA resin for additional purification. The decontamination factor for removal of uranium from plutonium for this method is greater than 1 x 10{sup 6}. Alpha spectrometry can also be applied so that the shorter-lived {sup 238}Pu isotope can be measured successfully. {sup 239}Pu, {sup 242}Pu and {sup 237}Np were measured by ICP-MS, while {sup 236}Pu and {sup 238}Pu were measured by alpha spectrometry.

  17. Analysis of quantization error in high-precision continuous-flow isotope ratio mass spectrometry.

    PubMed

    Sacks, Gavin L; Wolyniak, Christopher J; Brenna, J Thomas

    2003-12-12

    High-precision isotope ratio mass spectrometry (IRMS) systems are equipped with digitizers that deliver effective maximum digitization depths of 16 to 24 bits; however, there are no analyses of the proper board depth required to retain high precision in continuous-flow techniques. We report an experimental and theoretical evaluation of quantization error in continuous-flow IRMS (CF-IRMS). CO2 samples (100 pmol-30 nmol) were injected into a gas chromatography combustion IRMS system (GC-CIRMS). The analog signal was digitized by high precision, 24-bit ADC boards at 10 Hz, and was post-processed to simulate 12, 14, and 16-bit data sets. Delta13Cpdh values were calculated for all data sets by the conventional "summation" method or by curve-fitting the chromatographic peaks to the exponentially modified Gaussian (EMG) function. Benchmarks of S.D.(delta13Cpdh) = 0.3, 0.6, and 1.0/1000 were considered to assess precision. In the presence of significant quantization noise, curve-fitting required several-fold less CO2 than the summation method to reach a given benchmark. We derived an equation to describe the theoretical limitations of precision for the summation method as a function of CO2 admitted to the source and the step size of the boards. Theory was in close agreement with the observed lower limit of precision for the simulated 16-bit data set. Curve-fitting achieved a precision of S.D. <0.3/1000 for injections 20-fold smaller than summation for CO2 samples collected on an IRMS with 16-bit resolution. By mitigating the impact of quantization noise, curve-fitting expands the dynamic range within a single run to include lower analyte levels, and effectively reduces the need for high pumping capacities and high precision ADC boards. PMID:14661751

  18. Dansylation isotope labeling liquid chromatography mass spectrometry for parallel profiling of human urinary and fecal submetabolomes.

    PubMed

    Su, Xiaoling; Wang, Nan; Chen, Deying; Li, Yunong; Lu, Yingfeng; Huan, Tao; Xu, Wei; Li, Liang; Li, Lanjuan

    2016-01-15

    Human urine and feces can be non-invasively collected for metabolomics-based disease biomarker discovery research. Because urinary and fecal metabolomes are thought to be different, analysis of both biospecimens may generate a more comprehensive metabolomic profile that can be better related to the health state of an individual. Herein we describe a method of using differential chemical isotope labeling (CIL) liquid chromatography mass spectrometry (LC-MS) for parallel metabolomic profiling of urine and feces. Dansylation labeling was used to quantify the amine/phenol submetabolome changes among different samples based on (12)C-labeling of individual samples and (13)C-labeling of a pooled urine or pooled feces and subsequent analysis of the (13)C-/(12)C-labeled mixture by LC-MS. The pooled urine and pooled feces are further differentially labeled, mixed and then analyzed by LC-MS in order to relate the metabolite concentrations of the common metabolites found in both biospecimens. This method offers a means of direct comparison of urinary and fecal submetabolomes. We evaluated the analytical performance and demonstrated the utility of this method in the analysis of urine and feces collected daily from three healthy individuals for 7 days. On average, 2534 ± 113 (n = 126) peak pairs or metabolites could be detected from a urine sample, while 2507 ± 77 (n = 63) peak pairs were detected from a fecal sample. In total, 5372 unique peak pairs were detected from all the samples combined; 3089 and 3012 pairs were found in urine and feces, respectively. These results reveal that the urine and fecal metabolomes are very different, thereby justifying the consideration of using both biospecimens to increase the probability of finding specific biomarkers of diseases. Furthermore, the CIL LC-MS method described can be used to perform parallel quantitative analysis of urine and feces, resulting in more complete coverage of the human metabolome. PMID:26709303

  19. Determination of Polychlorinated Biphenyls in Solid Samples by Isotope Dilution Mass Spectrometry Using ³?Cl-Labeled Analogues.

    PubMed

    Somoano-Blanco, Lourdes; Rodriguez-Gonzalez, Pablo; García Fonseca, Sergio; Alonso, J Ignacio Garcia

    2015-08-01

    This work describes the first application of (37)Cl-labeled compounds to isotope dilution mass spectrometry (IDMS). The synthesis of 12 (37)Cl-labeled polychlorinated biphenyls (PCBs) was carried out by the chlorination of biphenyl with isotopically enriched chlorine gas, generated by the direct oxidation of Na(37)Cl with potassium peroxymonosulfate. After an exhaustive purification due to the presence of other congeners, the concentration and the isotopic enrichment of all (37)Cl-labeled PCBs in the mixture was determined. The proposed procedure allows the simultaneous quantification of every isotope diluted PCB congener in a single gas chromatography-tandem mass spectrometry (GC-MS/MS) injection without resorting to a methodological calibration graph. The results obtained here demonstrate that the use of (37)Cl-labeled analogues provides results in agreement with the certified values of three different Certified Reference Materials (marine sediment SRM 1944, fish tissue 1947, and loamy soil CRM 962-50) and analytical figures of merit comparable to those obtained using regular IDMS procedures based on the use of commercially available (13)C-labeled analogues. PMID:26165349

  20. Production of highly-enriched 134Ba for a reference material for isotope dilution mass spectrometry measurements

    DOE PAGESBeta

    Horkley, J. J.; Carney, K. P.; Gantz, E. M.; Davies, J. E.; Lewis, R. R.; Crow, J. P.; Poole, C. A.; Grimes, T. S.; Giglio, J. J.

    2015-03-17

    Isotope dilution mass spectrometry (IDMS) is an analytical technique capable of providing accurate and precise quantitation of trace isotope abundance and assay providing measurement uncertainties below 1 %. To achieve these low uncertainties, the IDMS method ideally utilizes chemically pure “spike” solutions that consist of a single highly enriched isotope that is well-characterized relating to the abundance of companion isotopes and concentration in solution. To address a current demand for accurate 137Cs/137Ba ratio measurements for “age” determination of radioactive 137Cs sources, Idaho National Laboratory (INL) is producing enriched 134Ba isotopes that are tobe used for IDMS spikes to accurately determinemore »137Ba accumulation from the decay of 137Cs. The final objective of this work it to provide a homogenous set of reference materials that the National Institute of Standards and Technology can certify as standard reference materials used for IDMS. The process that was developed at INL for the separation and isolation of Ba isotopes, chemical purification of the isotopes in solution, and the encapsulation of the materials will be described.« less

  1. Production of highly-enriched 134Ba for a reference material for isotope dilution mass spectrometry measurements

    SciTech Connect

    Horkley, J. J.; Carney, K. P.; Gantz, E. M.; Davies, J. E.; Lewis, R. R.; Crow, J. P.; Poole, C. A.; Grimes, T. S.; Giglio, J. J.

    2015-03-17

    Isotope dilution mass spectrometry (IDMS) is an analytical technique capable of providing accurate and precise quantitation of trace isotope abundance and assay providing measurement uncertainties below 1 %. To achieve these low uncertainties, the IDMS method ideally utilizes chemically pure “spike” solutions that consist of a single highly enriched isotope that is well-characterized relating to the abundance of companion isotopes and concentration in solution. To address a current demand for accurate 137Cs/137Ba ratio measurements for “age” determination of radioactive 137Cs sources, Idaho National Laboratory (INL) is producing enriched 134Ba isotopes that are tobe used for IDMS spikes to accurately determine 137Ba accumulation from the decay of 137Cs. The final objective of this work it to provide a homogenous set of reference materials that the National Institute of Standards and Technology can certify as standard reference materials used for IDMS. The process that was developed at INL for the separation and isolation of Ba isotopes, chemical purification of the isotopes in solution, and the encapsulation of the materials will be described.

  2. Production of highly-enriched 134Ba for a reference material for isotope dilution mass spectrometry measurements

    SciTech Connect

    J.J. Horkley; K.P E.M. Gantz; J.E. Davis; R.R. Lewis; J.P. Crow; C.A. Poole; T.S. Grimes; J.J. Giglio

    2015-03-01

    t Isotope dilution mass spectrometry (IDMS) is an analytical technique capable of providing accurate and precise quantitation of trace isotope abundance and assay providing measurement uncertainties below 1 %. To achieve these low uncertainties, the IDMS method ideally utilizes chemically pure ‘‘spike’’ solutions that consist of a single highly enriched isotope that is well-characterized relating to the abundance of companion isotopes and concentration in solution. To address a current demand for accurate 137Cs/137Ba ratio measurements for ‘‘age’’ determination of radioactive 137Cs sources, Idaho National Laboratory (INL) is producing enriched 134Ba isotopes that are tobe used for IDMS spikes to accurately determine 137Ba accumulation from the decay of 137Cs. The final objective of this work it to provide a homogenous set of reference materials that the National Institute of Standards and Technology can certify as standard reference materials used for IDMS. The process that was developed at INL for the separation and isolation of Ba isotopes, chemical purification of the isotopes in solution,

  3. Evaluation of the 34S/32S ratio of Soufre de Lacq elemental sulfur isotopic reference material by continuous flow isotope-ratio mass spectrometry

    USGS Publications Warehouse

    Qi, H.P.; Coplen, T.B.

    2003-01-01

    Soufre de Lacq elemental sulfur reference material (IAEA-S-4) isotopically is homogeneous in amounts as small as 41 ??g as determined by continuous flow isotope-ratio mass spectrometry. The ??34S value for this reference material is +16.90 ?? 0.12??? (1??) on a scale (Vienna Can??on Diablo troilite, VCDT) where IAEA-S-1 Ag2S is -0.3??? and IAEA-S-2 Ag2S is +22.67???. Published by Elsevier Science B.V.

  4. Caution on the use of liquid nitrogen traps in stable hydrogen isotope-ratio mass spectrometry

    USGS Publications Warehouse

    Coplen, Tyler B.; Qi, Haiping

    2010-01-01

    An anomalous stable hydrogen isotopic fractionation of 4 ‰ in gaseous hydrogen has been correlated with the process of adding liquid nitrogen (LN2) to top off the dewar of a stainless-steel water trap on a gaseous hydrogen-water platinum equilibration system. Although the cause of this isotopic fractionation is unknown, its effect can be mitigated by (1) increasing the capacity of any dewars so that they do not need to be filled during a daily analytic run, (2) interspersing isotopic reference waters among unknowns, and (3) applying a linear drift correction and linear normalization to isotopic results with a program such as Laboratory Information Management System (LIMS) for Light Stable Isotopes. With adoption of the above guidelines, measurement uncertainty can be substantially improved. For example, the long-term (months to years) ?2H reproducibility (1& sigma; standard deviation) of nine local isotopic reference waters analyzed daily improved substantially from about 1‰ to 0.58 ‰. This isotopically fractionating mechanism might affect other isotope-ratio mass spectrometers in which LN2 is used as a moisture trap for gaseous hydrogen

  5. Caution on the use of liquid nitrogen traps in stable hydrogen isotope-ratio mass spectrometry

    USGS Publications Warehouse

    Coplen, T.B.; Qi, H.

    2010-01-01

    An anomalous stable hydrogen isotopic fractionation of 4 ??? in gaseous hydrogen has been correlated with the process of adding liquid nitrogen (LN2) to top off the dewar of a stainless-steel water trap on a gaseous hydrogen-water platinum equilibration system. Although the cause of this isotopic fractionation is unknown, its effect can be mitigated by (1) increasing the capacity of any dewars so that they do not need to be filled during a daily analytic run, (2) interspersing isotopic reference waters among unknowns, and (3) applying a linear drift correction and linear normalization to isotopic results with a program such as Laboratory Information Management System (LIMS) for Light Stable Isotopes. With adoption of the above guidelines, measurement uncertainty can be substantially improved. For example, the long-term (months to years) ??2H reproducibility (1?? standard deviation) of nine local isotopic reference waters analyzed daily improved substantially from about 1 ??? to 0.58 ???. This isotopically fractionating mechanism might affect other isotope-ratio mass spectrometers in which LN2 is used as a moisture trap for gaseous hydrogen. ?? This article not subject to U.S. Copyright. Published 2010 by the American Chemical Society.

  6. Determination of lead, uranium, thorium, and thallium in silicate glass standard materials by isotope dilution mass spectrometry

    USGS Publications Warehouse

    Barnes, I.L.; Garner, E.L.; Gramlich, J.W.; Moore, L.J.; Murphy, T.J.; Machlan, L.A.; Shields, W.R.; Tatsumoto, M.; Knight, R.J.

    1973-01-01

    A set of four standard glasses has been prepared which have been doped with 61 different elements at the 500-, 50-, 1-, and 0.02-ppm level. The concentrations of lead, uranium, thorium, and thallium have been determined by isotope dilution mass spectrometry at a number of points in each of the glasses. The results obtained from independent determinations in two laboratories demonstrate the homogeneity of the samples and that precision of the order of 0.5% (95% L.E.) may be obtained by the method even at the 20-ppb level for these elements. The chemical and mass spectrometric procedures necessary are presented.

  7. Ion microscopy with resonant ionization mass spectrometry : time-of-flight depth profiling with improved isotopic precision.

    SciTech Connect

    Pellin, M. J.; Veryovkin, I. V.; Levine, J.; Zinovev, A.; Davis, A. M.; Stephan, T.; Tripa, C. E.; King, B. V.; Savina, M. R.

    2010-01-01

    There are four generally mutually exclusive requirements that plague many mass spectrometric measurements of trace constituents: (1) the small size (limited by the depth probed) of many interesting materials requires high useful yields to simply detect some trace elements, (2) the low concentrations of interesting elements require efficient discrimination from isobaric interferences, (3) it is often necessary to measure the depth distribution of elements with high surface and low bulk contributions, and (4) many applications require precise isotopic analysis. Resonant ionization mass spectrometry has made dramatic progress in addressing these difficulties over the past five years.

  8. Metabolic flux in carbohydrate biosynthesis. New methods using stable isotopes, mass spectrometry, and NMR

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Structural analysis of carbohydrates involves three parameters: composition, linkage, and conformation, and tends to rely on the various forms of two techniques; mass spectrometry (MS) and nuclear magnetic resonance (NMR) spectroscopy. These techniques are enhanced and extended by the use of stable...

  9. SILEC: a protocol for generating and using isotopically labeled coenzyme A mass spectrometry standards

    PubMed Central

    Basu, Sankha S; Blair, Ian A

    2013-01-01

    Stable isotope labeling by essential nutrients in cell culture (SILEC) was recently developed to generate isotopically labeled coenzyme A (CoA) and short-chain acyl-CoA thioesters. This was accomplished by modifying the widely used technique of stable isotope labeling by amino acids in cell culture to include [13C315N]-pantothenate (vitamin B5), a CoA precursor, instead of the isotopically labeled amino acids. The lack of a de novo pantothenate synthesis pathway allowed for efficient and near-complete labeling of the measured CoA species. This protocol provides a step-by-step approach for generating stable isotope-labeled short-chain acyl-CoA internal standards in mammalian and insect cells as well as instructions on how to use them in stable isotope dilution mass spectrometric-based analyses. Troubleshooting guidelines, as well as a list of unlabeled and labeled CoA species, are also included. This protocol represents a prototype for generating stable isotope internal standards from labeled essential nutrients such as pantothenate. The generation and use of SILEC standards takes approximately 2–3 weeks. PMID:22157971

  10. 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 optimise signal to noise ratios from low ion beam intensities on Faraday cups [2,3]. Data will be presented from the Thermo Scientific NEPTUNE Plus MC-ICP-MS, sampling sub-nanogram quantities of analyte from solution and by laser ablation. Faraday only measurements of sub-microgram analyte quantities will also be presented, using a 1012 ? amplifier for the minor isotope 234U. These data are compared to a dataset collected by a first generation MC-ICP-MS instrument, reported by Lloyd et al. [1]. [1] N. S. Lloyd, R. R. Parrish, M. S. A. Horstwood & S. R. N. Chenery, Journal of Analytical Atomic Spectrometry 24 (6), 752 (2009). [2] C. Bouman, J.B. Schwieters, M. Deerberg & D. Tuttas, Geochimica et Cosmochimica Acta 73 (13, Supplement 1) (2009). [3] D. Tuttas, J.B. Schwieters, & N.S. Lloyd, Geochimica et Cosmochimica Acta 74 (11, Supplement 1) (2010).

  11. The study of trace metal absoption using stable isotopes and mass spectrometry

    NASA Astrophysics Data System (ADS)

    Fennessey, P. V.; Lloyd-Kindstrand, L.; Hambidge, K. M.

    1991-12-01

    The absorption and excretion of zinc stable isotopes have been followed in more than 120 human subjects. The isotope enrichment determinations were made using a standard VG 7070E HF mass spectrometer. A fast atom gun (FAB) was used to form the ions from a dry residue on a pure silver probe tip. Isotope ratio measurements were found to have a precision of better than 2% (relative standard deviation) and required a sample size of 1-5 [mu]g. The average true absorption of zinc was found to be 73 ± 12% (2[sigma]) when the metal was taken in a fasting state. This absorption figure was corrected for tracer that had been absorbed and secreted into the gastrointestinal (GI) tract over the time course of the study. The average time for a majority of the stable isotope tracer to pass through the GI tract was 4.7 ± 1.9 (2[sigma]) days.

  12. Quantifying Uranium Isotope Ratios Using Resonance Ionization Mass Spectrometry: The Influence of Laser Parameters on Relative Ionization Probability

    SciTech Connect

    Isselhardt, B H

    2011-09-06

    Resonance Ionization Mass Spectrometry (RIMS) has been developed as a method to measure relative uranium isotope abundances. In this approach, RIMS is used as an element-selective ionization process to provide a distinction between uranium atoms and potential isobars without the aid of chemical purification and separation. We explore the laser parameters critical to the ionization process and their effects on the measured isotope ratio. Specifically, the use of broad bandwidth lasers with automated feedback control of wavelength was applied to the measurement of {sup 235}U/{sup 238}U ratios to decrease laser-induced isotopic fractionation. By broadening the bandwidth of the first laser in a 3-color, 3-photon ionization process from a bandwidth of 1.8 GHz to about 10 GHz, the variation in sequential relative isotope abundance measurements decreased from >10% to less than 0.5%. This procedure was demonstrated for the direct interrogation of uranium oxide targets with essentially no sample preparation. A rate equation model for predicting the relative ionization probability has been developed to study the effect of variation in laser parameters on the measured isotope ratio. This work demonstrates that RIMS can be used for the robust measurement of uranium isotope ratios.

  13. Modified ion exchange separation for tungsten isotopic measurements from kimberlite samples using multi-collector inductively coupled plasma mass spectrometry.

    PubMed

    Sahoo, Yu Vin; Nakai, Shun'ichi; Ali, Arshad

    2006-03-01

    Tungsten isotope composition of a sample of deep-seated rock can record the influence of core-mantle interaction of the parent magma. Samples of kimberlite, which is known as a carrier of diamond, from the deep mantle might exhibit effects of core-mantle interaction. Although tungsten isotope anomaly was reported for kimberlites from South Africa, a subsequent investigation did not verify the anomaly. The magnesium-rich and calcium-rich chemical composition of kimberlite might engender difficulty during chemical separation of tungsten for isotope analyses. This paper presents a simple, one-step anion exchange technique for precise and accurate determination of tungsten isotopes in kimberlites using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). Large quantities of Ca and Mg in kimberlite samples were precipitated and removed with aqueous H(2)SO(4). Highly pure fractions of tungsten for isotopic measurements were obtained following an anion exchange chromatographic procedure involving mixed acids. That procedure enabled efficient removal of high field strength elements (HFSE), such as Hf, Zr and Ti, which are small ions that carry strong charges and develop intense electrostatic fields. The tungsten yields were 85%-95%. Advantages of this system include less time and less use of reagents. Precise and accurate isotopic measurements are possible using fractions of tungsten that are obtained using this method. The accuracy and precision of these measurements were confirmed using various silicate standard rock samples, JB-2, JB-3 and AGV-1. PMID:16496054

  14. High-precision measurement of variations in calcium isotope ratios in urine by multiple collector inductively coupled plasma mass spectrometry

    USGS Publications Warehouse

    Morgan, J.L.L.; Gordon, G.W.; Arrua, R.C.; Skulan, J.L.; Anbar, A.D.; Bullen, T.D.

    2011-01-01

    We describe a new chemical separation method to isolate Ca from other matrix elements in biological samples, developed with the long-term goal of making high-precision measurement of natural stable Ca isotope variations a clinically applicable tool to assess bone mineral balance. A new two-column procedure utilizing HBr achieves the purity required to accurately and precisely measure two Ca isotope ratios (44Ca/42Ca and 44Ca/43Ca) on a Neptune multiple collector inductively coupled plasma mass spectrometer (MC-ICPMS) in urine. Purification requirements for Sr, Ti, and K (Ca/Sr > 10000; Ca/Ti > 10000000; and Ca/K > 10) were determined by addition of these elements to Ca standards of known isotopic composition. Accuracy was determined by (1) comparing Ca isotope results for samples and standards to published data obtained using thermal ionization mass spectrometry (TIMS), (2) adding a Ca standard of known isotopic composition to a urine sample purified of Ca, and (3) analyzing mixtures of urine samples and standards in varying proportions. The accuracy and precision of ?44/42Ca measurements of purified samples containing 25 ?g of Ca can be determined with typical errors less than ±0.2‰ (2?).

  15. Determination of the sulfur isotope ratio in carbonyl sulfide using gas chromatography/isotope ratio mass spectrometry on fragment ions 32S+, 33S+, and 34S+.

    PubMed

    Hattori, Shohei; Toyoda, Akari; Toyoda, Sakae; Ishino, Sakiko; Ueno, Yuichiro; Yoshida, Naohiro

    2015-01-01

    Little is known about the sulfur isotopic composition of carbonyl sulfide (OCS), the most abundant atmospheric sulfur species. We present a promising new analytical method for measuring the stable sulfur isotopic compositions (?(33)S, ?(34)S, and ?(33)S) of OCS using nanomole level samples. The direct isotopic analytical technique consists of two parts: a concentration line and online gas chromatography-isotope ratio mass spectrometry (GC-IRMS) using fragmentation ions (32)S(+), (33)S(+), and (34)S(+). The current levels of measurement precision for OCS samples greater than 8 nmol are 0.42‰, 0.62‰, and 0.23‰ for ?(33)S, ?(34)S, and ?(33)S, respectively. These ? and ? values show a slight dependence on the amount of injected OCS for volumes smaller than 8 nmol. The isotope values obtained from the GC-IRMS method were calibrated against those measured by a conventional SF6 method. We report the first measurement of the sulfur isotopic composition of OCS in air collected at Kawasaki, Kanagawa, Japan. The ?(34)S value obtained for OCS (4.9 ± 0.3‰) was lower than the previous estimate of 11‰. When the ?(34)S value for OCS from the atmospheric sample is postulated as the global signal, this finding, coupled with isotopic fractionation for OCS sink reactions in the stratosphere, explains the reported ?(34)S for background stratospheric sulfate. This suggests that OCS is a potentially important source for background (nonepisodic or nonvolcanic) stratospheric sulfate aerosols. PMID:25439590

  16. The use of stable isotopes and gas chromatography/mass spectrometry in the identification of steroid metabolites in the equine

    SciTech Connect

    Houghton, E.; Dumasia, M.C.; Teale, P.; Smith, S.J.; Cox, J.; Marshall, D.; Gower, D.B. )

    1990-10-01

    Stable isotope gas chromatography/mass spectrometry has been used successfully in the elucidation of structures of urinary steroid metabolites in the horse and in the identification of metabolites isolated from in vivo perfusion and in vitro incubation studies using equine tissue preparations. Deuterium-labeled steroids, testosterone, dehydroepiandrosterone, and 5-androstene-3 beta,17 beta-diol have been synthesized by base-catalyzed isotope exchange methods and the products characterized by gas chromatography/mass spectrometry. (16,16(-2)H2)Dehydroepiandrosterone (plus radiolabeled dehydroepiandrosterone) was perfused into a testicular artery of a pony stallion and was shown to be metabolized into 2H2-labeled testosterone, 4-androstenedione, isomers of 5-androstene-3,17-diol, 19-hydroxytestosterone, and 19-hydroxy-4-androstenedione. In further studies, equine testicular minces have been incubated with 2H2-labeled and radiolabeled dehydroepiandrosterone and 5-androstene-3 beta, 17 beta-diol. The metabolites, whose identity was confirmed by stable isotope gas chromatography/mass spectrometry, proved the interconversion of the two substrates, as well as formation of testosterone and 4-androstenedione. The aromatization of dehydroepiandrosterone was also confirmed, together with the formation of an isomer of 5(10)-estrene-3,17-diol from both substrates showing 19-demethylation without concomitant aromatization. In studies of the feto-placental unit, the allantochorion was shown to aromatize (2H5)testosterone to (2H4)estradiol, the loss of one 2H from the substrate being consistent with aromatization of the A ring. The formation of 6-hydroxyestradiol was also confirmed in this study. The same technique has been valuable in determining the structure of two metabolites of nandrolone isolated from horse urine.

  17. A method for determining isotopic composition of elements by thermal ionization source mass spectrometry: Application to strontium

    NASA Astrophysics Data System (ADS)

    Cavazzini, Giancarlo

    2005-01-01

    It is shown that in thermal ionization source mass spectrometry, if isotope fractionation of the element in the sample follows a linear law, straight-line distributions in xm versus xm/ym diagrams are observed, where xm and ym are two measured isotope ratios. The slopes and y-intercepts of these linear distributions are functions of the [`]true' (starting) values xt and yt of the element in the sample and of the masses of the isotopes involved in ratios x and y. Since the masses of the nuclides are known, true ratios xt and yt can be calculated. This theoretical result is used to determine the non-radiogenic part of the isotopic composition of strontium in NBS SRM 987, one 84Sr-enriched isotopic tracer prepared at the Oak Ridge National Laboratory, and two natural samples (rocks from the metamorphic basement of the Italian Eastern Alps) without any assumption about the isotopic composition itself. Strontium was loaded as nitrate on single tungsten filaments, and 88Sr/86Sr and 84Sr/86Sr ratios were measured up to a fractionation of ~1% u-1 in a single-collector VG 54E mass spectrometer. For each run, 86Sr/88Sr, 84Sr/86Sr and 84Sr/88Sr ratios were calculated for all useful xm versus xm/ym distributions. The respective weighted average values are considered the true values of the isotope ratios in the sample. Four runs of isotopic standard NBS SRM 987 and one run of the isotopic tracer gave accurate and reproducible results which are identical, within error limits, to the respective certified values. The four determinations of NBS 987 resulted in the following weighted average values: 86Sr/88Sr = 0.11942 +/- 0.00018; 84Sr/86Sr = 0.056485 +/- 0.000075; 84Sr/88Sr = 0.006746 +/- 0.000017 (error at 2[sigma] level). The values of the natural 86Sr/88Sr ratio (two rocks: 0.11956 +/- 0.00017 and 0.11957 +/- 0.00008; NBS 987: 0.11942 +/- 0.00018) are identical within error limits, and identical or very close to the recommended value of 0.1194, the worldwide assumed [`]true' 86Sr/88Sr value in the commonly used procedure of determining 87Sr/86Sr ratio by normalization. However, due to the accuracy of the above determinations, it is suggested that, in nature, significant differences exist in the non-radiogenic part of the isotopic composition of strontium.

  18. Mass spectrometry with accelerators.

    PubMed

    Litherland, A E; Zhao, X-L; Kieser, W E

    2011-01-01

    As one in a series of articles on Canadian contributions to mass spectrometry, this review begins with an outline of the history of accelerator mass spectrometry (AMS), noting roles played by researchers at three Canadian AMS laboratories. After a description of the unique features of AMS, three examples, (14)C, (10)Be, and (129)I are given to illustrate the methods. The capabilities of mass spectrometry have been extended by the addition of atomic isobar selection, molecular isobar attenuation, further ion acceleration, followed by ion detection and ion identification at essentially zero dark current or ion flux. This has been accomplished by exploiting the techniques and accelerators of atomic and nuclear physics. In 1939, the first principles of AMS were established using a cyclotron. In 1977 the selection of isobars in the ion source was established when it was shown that the (14)N(-) ion was very unstable, or extremely difficult to create, making a tandem electrostatic accelerator highly suitable for assisting the mass spectrometric measurement of the rare long-lived radioactive isotope (14)C in the environment. This observation, together with the large attenuation of the molecular isobars (13)CH(-) and (12)CH?2(-) during tandem acceleration and the observed very low background contamination from the ion source, was found to facilitate the mass spectrometry of (14)C to at least a level of (14)C/C ~ 6 × 10(-16), the equivalent of a radiocarbon age of 60,000 years. Tandem Accelerator Mass Spectrometry, or AMS, has now made possible the accurate radiocarbon dating of milligram-sized carbon samples by ion counting as well as dating and tracing with many other long-lived radioactive isotopes such as (10)Be, (26)Al, (36)Cl, and (129)I. The difficulty of obtaining large anion currents with low electron affinities and the difficulties of isobar separation, especially for the heavier mass ions, has prompted the use of molecular anions and the search for alternative methods of isobar separation. These techniques are discussed in the latter part of the review. PMID:22031277

  19. Osmium isotopic ratio measurements by inductively coupled plasma source mass spectrometry

    SciTech Connect

    Russ, G.P. III; Bazan, J.M.; Date, A.R.

    1987-04-01

    The isotopic composition of nanogram quantities of osmium was measured by using an inductively coupled plasma source mass spectrometer. Sensitivity was enhanced a factor of approx.100 by the use of an osmium tetraoxide vapor generator rather than nebulization of solution. For samples less than or equal to5 ng, the ratios /sup 190/Os//sup 192/Os, /sup 189/Os//sup 192/Os, and /sup 188/Os//sup 192/Os were determined to better than +/- 0.5% (1sigma/sub m/) precision. For the minor isotopes, the ratios /sup 187/Os//sup 192/Os and /sup 186/Os//sup 192/Os were determined to +/-1%, and /sup 184/Os//sup 192/Os (4 x 10/sup -4/) was determined to approx.10%. Isotope ratios for common osmium are reported.

  20. Precise ruthenium fission product isotopic analysis using dynamic reaction cell inductively coupled plasma mass spectrometry (DRC-ICP-MS)

    SciTech Connect

    Brown, Christopher F.; Dresel, P. Evan; Geiszler, Keith N.; Farmer, Orville T.

    2006-05-09

    99Tc is a subsurface contaminant of interest at numerous federal, industrial, and international facilities. However, as a mono-isotopic fission product, 99Tc lacks the ability to be used as a signature to differentiate between the different waste disposal pathways that could have contributed to subsurface contamination at these facilities. Ruthenium fission-product isotopes are attractive analogues for the characterization of 99Tc sources because of their direct similarity to technetium with regard to subsurface mobility, and their large fission yields and low natural background concentrations. We developed an inductively coupled plasma mass spectrometry (ICP-MS) method capable of measuring ruthenium isotopes in groundwater samples and extracts of vadose zone sediments. Samples were analyzed directly on a Perkin Elmer ELAN DRC II ICP-MS after a single pass through a 1-ml bed volume of Dowex AG 50W-X8 100-200 mesh cation exchange resin. Precise ruthenium isotopic ratio measurements were achieved using a low-flow Meinhard-type nebulizer and long sample acquisition times (150,000 ms). Relative standard deviations of triplicate replicates were maintained at less than 0.5% when the total ruthenium solution concentration was 0.1 ng/ml or higher. Further work was performed to minimize the impact caused by mass interferences using the dynamic reaction cell (DRC) with O2 as the reaction gas. The aqueous concentrations of 96Mo and 96Zr were reduced by more than 99.7% in the reaction cell prior to injection of the sample into the mass analyzer quadrupole. The DRC was used in combination with stable-mass correction to quantitatively analyze samples containing up to 2-orders of magnitude more zirconium and molybdenum than ruthenium. The analytical approach documented herein provides an efficient and cost-effective way to precisely measure ruthenium isotopes and quantitate total ruthenium (natural vs. fission-product) in aqueous matrixes.

  1. Evidence for a possible dietary effect on the isotopic composition of Zn in blood via isotopic analysis of food products by multi-collector ICP-mass spectrometry.

    PubMed

    Costas-Rodríguez, Marta; Van Heghe, Lana; Vanhaecke, Frank

    2014-01-01

    In this work, the hypothesis of a possible dietary effect on the isotopic composition of Zn in blood from populations with different feeding habits, i.e. lacto-ovo vegetarians and omnivores, was investigated through isotopic analysis of Zn in common food products by multi-collector ICP - mass spectrometry (MC-ICP-MS). Several certified reference materials (CRMs) were also included in the sample set for comparison purposes. For these CRMs, the isotopic composition of Zn is expressed as ?-values, calculated with respect to both IRMM-3702 and JMC-ZnLyon, as isotopic standards. The range of ?(66)Zn values observed in food products was approximately 1.9‰. In general, vegetables, cereals and derived products showed an enrichment of the heavier Zn isotopes, whereas a depletion was observed in products of animal origin (meat, fish, egg and semi-skimmed milk), relative to human blood samples. Mussel, however, showed a significant enrichment of the heavier isotopes, which is hypothetically attributed to its accumulation behaviour. Thus, the lower ?(66)Zn values found in food products of animal origin appear to be reflected in the lower ?(66)Zn value observed in blood from an omnivorous population compared to that for a vegetarian population. PMID:24196216

  2. Mass spectrometry

    SciTech Connect

    Burlingame, A.L.; Maltby, D.; Russell, D.H.; Holland, P.T.

    1988-06-15

    This review series has served as a timely means to provide critical discussion of the advances and directions, strengths and weaknesses, and the state of maturity and promise of both new and established strategies and methods in a unifying single source. Widely disparate discoveries, inventions, and purposeful developments are required to enable mass spectrometric based strategies to take hold and make inroads into new types of issues at the molecular level of biological, medical, and chemical sciences. These are interdisciplinary endeavors. Of necessity, they have been selective both in the topics covered and in the contributions included but have endeavored to be sufficiently general so that both the new reader and the expert might readily find further literature and necessary detail. They have attempted to provide a thematic context for each topic. They note that this review series has a cumulative continuity about it, and the previous few Overview sections are still timely.

  3. Delta13C stable isotope analysis of atmospheric oxygenated volatile organic compounds by gas chromatography-isotope ratio mass spectrometry.

    PubMed

    Giebel, Brian M; Swart, Peter K; Riemer, Daniel D

    2010-08-15

    We present a new method for analyzing the delta(13)C isotopic composition of several oxygenated volatile organic compounds (OVOCs) from direct sources and ambient atmospheric samples. Guided by the requirements for analysis of trace components in air, a gas chromatograph isotope ratio mass spectrometer (GC-IRMS) system was developed with the goal of increasing sensitivity, reducing dead-volume and peak band broadening, optimizing combustion and water removal, and decreasing the split ratio to the isotope ratio mass spectrometer (IRMS). The technique relies on a two-stage preconcentration system, a low-volume capillary reactor and water trap, and a balanced reference gas delivery system. The instrument's measurement precision is 0.6 to 2.9 per thousand (1sigma), and results indicate that negligible sample fractionation occurs during gas sampling. Measured delta(13)C values have a minor dependence on sample size; linearity for acetone was 0.06 per thousand ng C(-1) and was best over 1-10 ng C. Sensitivity is approximately 10 times greater than similar instrumentation designs, incorporates the use of a diluted working reference gas (0.1% CO(2)), and requires collection of >0.7 ng C to produce accurate and precise results. With this detection limit, a 1.0 L sample of ambient air provides sufficient carbon for isotopic analysis. Emissions from vegetation and vehicle exhaust are compared and show clear differences in isotopic signatures. Ambient samples collected in metropolitan Miami and the Everglades National Park can be differentiated and reflect multiple sources and sinks affecting a single sampling location. Vehicle exhaust emissions of ethanol, and those collected in metropolitan Miami, have anomalously enriched delta(13)C values ranging from -5.0 to -17.2 per thousand; we attribute this result to ethanol's origin from corn and use as an additive in automotive fuels. PMID:20704369

  4. Stable isotope dilution gas chromatography-mass spectrometry for quantification of thymoquinone in black cumin seed oil.

    PubMed

    Johnson-Ajinwo, Okiemute Rosa; Li, Wen-Wu

    2014-06-18

    Black cumin seed (Nigella sativa L.) is a widely used spice and herb, where thymoquinone (2-isopropyl-5-methyl-1,4-benzoquinone) is the major bioactive compound. Here, a stable isotope dilution (SID) gas chromatography-mass spectrometry (GC-MS) technique was developed for the quantification of thymoquinone. A doubly deuterated thymoquinone ([(2)H2]-thymoquinone) was synthesized for the first time with more than 93% deuteration degree shown by mass spectrometry and proton nuclear magnetic resonance ((1)H NMR). This compound was used as an internal standard for the quantification of thymoquinone using a SID GC-MS method. The validation experiment showed a recovery rate of 99.1 ± 1.1% relative standard deviation (RSD). Standard addition and external calibration methods have also been used to quantify thymoquinone, which cross-validated the developed stable isotope dilution assay (SIDA). In comparison to external calibration and standard addition methods, the SIDA method is robust and accurate. The concentration of thymoquinone in five marketed black cumin seed oils ranged between 3.34 and 10.8 mg/mL by use of SID GC-MS. PMID:24871868

  5. Performance and optimization of a combustion interface for isotope ratio monitoring gas chromatography/mass spectrometry

    NASA Technical Reports Server (NTRS)

    Merritt, D. A.; Freeman, K. H.; Ricci, M. P.; Studley, S. A.; Hayes, J. M.

    1995-01-01

    Conditions and systems for on-line combustion of effluents from capillary gas chromatographic columns and for removal of water vapor from product streams were tested. Organic carbon in gas chromatographic peaks 15 s wide and containing up to 30 nanomoles of carbon was quantitatively converted to CO2 by tubular combustion reactors, 200 x 0.5 mm, packed with CuO or NiO. No auxiliary source of O2 was required because oxygen was supplied by metal oxides. Spontaneous degradation of CuO limited the life of CuO reactors at T > 850 degrees C. Since NiO does not spontaneously degrade, its use might be favored, but Ni-bound carbon phases form and lead to inaccurate isotopic results at T < 1050 degrees C if gas-phase O2 is not added. For all compounds tested except CH4, equivalent isotopic results are provided by CuO at 850 degrees C, NiO + O2 (gas-phase mole fraction, 10(-3)) at 1050 degrees C and NiO at 1150 degrees C. The combustion interface did not contribute additional analytical uncertainty, thus observed standard deviations of 13C/12C ratios were within a factor of 2 of shot-noise limits. For combustion and isotopic analyses of CH4, in which quantitative combustion required T approximately 950 degrees C, NiO-based systems are preferred, and precision is approximately 2 times lower than that observed for other analytes. Water must be removed from the gas stream transmitted to the mass spectrometer or else protonation of CO2 will lead to inaccuracy in isotopic analyses. Although thresholds for this effect vary between mass spectrometers, differential permeation of H2O through Nafion tubing was effective in both cases tested, but the required length of the Nafion membrane was 4 times greater for the more sensitive mass spectrometer.

  6. Adsorption in gas mass spectrometry. I. Effects on the measurement of individual isotopic species

    NASA Astrophysics Data System (ADS)

    Gonfiantini, Roberto; Valkiers, Staf; Taylor, Philip D. P.; de Bièvre, Paul

    1997-05-01

    The adsorption-desorption process of gas molecules on the walls of the mass spectrometer inlet system was studied in order to assess quantitatively its influence on measurement results. The effects on individual isotopic species in SiF4 measurements required for the re-determination of the Avogadro constant are discussed in this paper, while the effects on isotope amount ratio determinations will be discussed in a companion paper. A model based on the Langmuir adsorption isotherm is developed, which fits well the experimental observations and provides the means to investigate adsorption and desorption kinetics in the inlet system. A parameter called the [`]apparent leak-rate coefficient' is introduced; this represents the relative variation with time of any isotopic species in the inlet system. All the adsorption parameters appearing in the balance equations are derived from the apparent leak-rate coefficient. Application of the model to long mass-spectrometric measurements of SiF4 yields a rate constant of 6.5 × 10-5 s-1 for SiF4 effusion through the molecular leak of the inlet system. Adsorption and desorption rate-constants are equal to 20-25% of the leak rate-constant, and the adsorption sites are about two orders of magnitude lower than the number of Ni and Cu atoms present on the inlet system walls.

  7. Accuracy and Reproducibility in Quantification of Plasma Protein Concentrations by Mass Spectrometry without the Use of Isotopic Standards

    PubMed Central

    Kramer, Gertjan; Woolerton, Yvonne; van Straalen, Jan P.; Vissers, Johannes P. C.; Dekker, Nick; Langridge, James I.; Beynon, Robert J.; Speijer, Dave; Sturk, Auguste; Aerts, Johannes M. F. G.

    2015-01-01

    Background Quantitative proteomic analysis with mass spectrometry holds great promise for simultaneously quantifying proteins in various biosamples, such as human plasma. Thus far, studies addressing the reproducible measurement of endogenous protein concentrations in human plasma have focussed on targeted analyses employing isotopically labelled standards. Non-targeted proteomics, on the other hand, has been less employed to this end, even though it has been instrumental in discovery proteomics, generating large datasets in multiple fields of research. Results Using a non-targeted mass spectrometric assay (LCMSE), we quantified abundant plasma proteins (43 mg/mL—40 ug/mL range) in human blood plasma specimens from 30 healthy volunteers and one blood serum sample (ProteomeXchange: PXD000347). Quantitative results were obtained by label-free mass spectrometry using a single internal standard to estimate protein concentrations. This approach resulted in quantitative results for 59 proteins (cut off ?11 samples quantified) of which 41 proteins were quantified in all 31 samples and 23 of these with an inter-assay variability of ? 20%. Results for 7 apolipoproteins were compared with those obtained using isotope-labelled standards, while 12 proteins were compared to routine immunoassays. Comparison of quantitative data obtained by LCMSE and immunoassays showed good to excellent correlations in relative protein abundance (r = 0.72–0.96) and comparable median concentrations for 8 out of 12 proteins tested. Plasma concentrations of 56 proteins determined by LCMSE were of similar accuracy as those reported by targeted studies and 7 apolipoproteins quantified by isotope-labelled standards, when compared to reference concentrations from literature. Conclusions This study shows that LCMSE offers good quantification of relative abundance as well as reasonable estimations of concentrations of abundant plasma proteins. PMID:26474480

  8. Discrimination of geographical origin of lentils (Lens culinaris Medik.) using isotope ratio mass spectrometry combined with chemometrics.

    PubMed

    Longobardi, F; Casiello, G; Cortese, M; Perini, M; Camin, F; Catucci, L; Agostiano, A

    2015-12-01

    The aim of this study was to predict the geographic origin of lentils by using isotope ratio mass spectrometry (IRMS) in combination with chemometrics. Lentil samples from two origins, i.e. Italy and Canada, were analysed obtaining the stable isotope ratios of ?(13)C, ?(15)N, ?(2)H, ?(18)O, and ?(34)S. A comparison between median values (U-test) highlighted statistically significant differences (p<0.05) for all isotopic parameters between the lentils produced in these two different geographic areas, except for ?(15)N. Applying principal component analysis, grouping of samples was observed on the basis of origin but with overlapping zones; consequently, two supervised discriminant techniques, i.e. partial least squares discriminant analysis and k-nearest neighbours algorithm were used. Both models showed good performances with external prediction abilities of about 93% demonstrating the suitability of the methods developed. Subsequently, isotopic determinations were also performed on the protein and starch fractions and the relevant results are reported. PMID:26041202

  9. Curve fitting for restoration of accuracy for overlapping peaks in gas chromatography/combustion isotope ratio mass spectrometry.

    PubMed

    Goodman, K J; Brenna, J T

    1994-04-15

    The effect of graded degrees of overlap on high-precision and -accuracy carbon isotope ratios determined by gas chromatography/combustion isotope ratio mass spectrometry (GCC/IRMS) is reported. Overlapping peaks of closely matched isotope ratio (difference delta 13CPDB < 1%) were analyzed by the conventional vertical drop summation algorithm and by curve fitting using the Levenberg-Marquardt algorithm. The conventional algorithm resulted in systematic bias related to degree of overlap even though precision was not noticeably affected. The exponentially modified Gaussian (EMG) and HaarhoffVanderLinde (HVL) functions were found to model GCC/IRMS peaks satisfactorily. Useful models over a wide range of overlap were obtained by applying consecutive HVL/HVL or HVL/EMG functions to overlapping peaks. Accuracy was improved in most cases and was never degraded. This study demonstrates the presence of subtle bias in isotope ratio determinations of overlapping peaks and the ability of automated curve fitting to compensate for these biases. PMID:8210045

  10. Determination of Mineral-Specific Clumped Isotope Acid Digestion Fractionation Factors Using Heating Experiments and Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Henry, D.; Tang, J.; Mosenfelder, J. L.; Eagle, R.; Tripati, A.

    2014-12-01

    Clumped isotope thermometry involves the determination of formation temperatures of carbonates from the fraction of isotopologues containing multiple rare isotopes (oxygen-18 and carbon-13). At high temperatures, the abundance of these isotopologues should be stochastic. At lower temperatures, there is a tendency for heavy isotopes to form bonds with each other. However, spectroscopic determination of isotope ratios with high precision is difficult in solids, and so 13C-18O bond abundance is not measured in the solid phase. Instead, analysis of carbonates is performed using gas source mass spectrometry, by reacting the carbonate samples with phosphoric acid and measuring the evolved CO2 gas. As an oxygen atom is lost during the conversion of CO32- groups to CO2, this reaction is hypothesized to result in mineral and acid digestion temperature-dependent fractionation. In order to quantify this fractionation between CO32- and CO2, this experiment seeks to determine acid fractionation factors for carbonate samples of varying composition by randomizing samples through intense heating and comparing analyte CO2 measured composition to the expected composition for a stochastically distributed sample. From this analysis, future carbonate measurements can be calibrated to account for acid digestion fractionation.

  11. A comparison of lead-isotope measurements on exploration-type samples using inductively coupled plasma and thermal ionization mass spectrometry

    USGS Publications Warehouse

    Gulson, B.L.; Meier, A.L.; Church, S.E.; Mizon, K.J.

    1989-01-01

    Thermal ionization mass spectrometry (TI-MS) has long been the method of choice for Pb-isotope determinations. More recently, however, inductively coupled plasma mass spectrometry (ICP-MS) has been used to determine Pb-isotope ratios for mineral exploration. The ICP-MS technique, although not as precise as TI-MS, may promote a wider application of Ph-isotope ratio methods because it allows individual isotopes to be determined more rapidly, generally without need for chemical separation (e.g., Smith et al., 1984; Hinners et al., 1987). To demonstrate the utility of the ICP-MS method, we have conducted a series of Pb-isotope measurements on several suites of samples using both TI-MS and ICP-MS. ?? 1989.

  12. Alternative Methodology for Boron Isotopic Analysis of CaCO3 by Negative Thermal Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Dwyer, G. S.; Vengosh, A.

    2012-12-01

    Negative thermal ionization mass spectrometry (NTIMS) has been a common tool for investigating boron isotopes in CaCO3 and other environmental samples, the high sensitivity of BO2- ionization enabling measurements of ng levels of boron. However, B isotope measurement by this technique suffers from a number of problems, including: (1) fractionation induced by selective ionization of B isotopes in the mass spectrometer; (2) CNO- interference on mass 42 ([10BO2]-) that may be present in some filament load solutions (such as B-free seawater processed through ion-exchange resin), and (3) potential matrix effects due to widely differing chemistry of samples and standards. Here we examine a potentially improved NTIMS methodology that incudes removal of sample-related calcium (and other cations) by ion exchange and uses an alternative filament loading solution prepared from high-purity single-element solutions of Ca, Mg, Na, and K. Initial results suggest that this new method may offer significant improvement over the more traditional NTIMS approach in which digested CaCO3 samples are directly loaded onto filaments in B-free seawater. Replicate analyses of standards and samples yield a typical standard deviation of approximately 0.3‰ ?11B and boron isotopic compositions comparable to reported or consensus values. Fractionation during analysis has thus far typically been less than 0.5‰ ?11B. The method delivers boron ionization efficiency similar to directly-loaded seawater, and negligible signal at mass 26 (CN-), a proxy for the possible interfering molecular CNO- ion. Standards and samples behave similarly and predictably during filament heating and analysis, thus allowing for fully automated data acquisition, which in turn may increase sample throughput and reduce potential analytical inconsistencies associated with operator-controlled heating and analysis.

  13. Authenticity of carbon dioxide bubbles in French ciders through multiflow-isotope ratio mass spectrometry measurements.

    PubMed

    Gaillard, Laetitia; Guyon, Francois; Salagoïty, Marie-Hélène; Médina, Bernard

    2013-12-01

    A procedure to detect whether carbon dioxide was added to French ciders has been developed. For this purpose, an optimised and simplified method is proposed to determine (13)C/(12)C isotope ratio of carbon dioxide (?(13)C) in ciders. Three critical steps were checked: (1) influence of atmospheric CO2 remaining in the loaded vial, (2) impact of helium flush, (3) sampling speed. This study showed that atmospheric CO2 does not impact the measurement, that helium flush can lead to isotopic fractionation and finally, that a fractionation occurs only 5h after bottle opening. The method, without any other preparation, consists in sampling 0.2 mL of cold (4 °C) cider in a vial that is passed in an ultrasonic bath for 10 min at room temperature to enhance cider de-carbonation. The headspace CO2 is then analysed using the link Multiflow®-isotope ratio mass spectrometer. Each year, a data bank is developed by fermenting authentic apples juices in order to control cider authenticity. Over a four year span (2008-2011), the CO2 produced during the fermentation step was studied. This set of 61 authentic ciders, from various French production areas, was used to determine a ?(13)C value range of -22.59±0.92‰ for authentic ciders CO2 bubbles. 75 commercial ciders were analysed with this method. Most of the samples analysed present a gas ?(13)C value in the expected range. Nevertheless, some ciders have ?(13)C values outside the 3? limit, revealing carbonation by technical CO2. This practice is not allowed for organic, "Controlled Appellation of Origin" ciders and ciders specifying natural carbonation on the label. PMID:23870934

  14. Histone H4 Acetylation Dynamics Determined by Stable Isotope Labeling with Amino Acids in Cell Culture and Mass Spectrometry

    PubMed Central

    Su, Xiaodan; Zhang, Liwen; Lucas, David M.; Davis, Melanie E.; Knapp, Amy R.; Green-Church, Kari B.; Marcucci, Guido; Parthun, Mark R.; Byrd, John C.; Freitas, Michael A.

    2007-01-01

    This paper describes an integrated approach that couples Stable Isotope Labeling with Amino Acids in Cell Culture (SILAC) to Acetic acid-Urea Polyacrylamide Gel Electrophoresis (AU-PAGE) and Matrix Assisted Laser Desorption/Ionization Time-of-Flight mass spectrometry (MALDI-TOF MS) for the quantitation and dynamics of histone H4 acetylation. The 697 acute lymphoblastic cell lines were grown in regular media (Lys-D0) and media in which lysine was substituted with deuterium-labeled lysine (Lys-D4). HDAC activity was inhibited by addition of the HDAC inhibitor depsipeptide to the culture media for different exposure times. Histones were extracted from cells pooled from unlabeled, untreated cells and labeled, treated cells, followed by AU-PAGE separation. Gel bands corresponding to different acetylation states of H4 were excised, in-gel digested with trypsin, and analyzed by MALDI-TOF mass spectrometry. Detailed information was obtained for both the change of histone H4 acetylation specific to N-terminus and global transformation of H4 from one acetylation state to another following treatment with the HDAC inhibitor depsipeptide. The kinetics of H4 acetylation was also assessed. The current study provides quantitative basis for developing potential therapies by using epigenetic regulation and the developed methodology can be applied to quantitation of change for other histone modifications induced by external stimuli. PMID:17286952

  15. Surfactant protein C metabolism in human infants and adult patients by stable isotope tracer and mass spectrometry.

    PubMed

    Simonato, Manuela; Baritussio, Aldo; Pioselli, Barbara; Ori, Carlo; Catinella, Silvia; Carnielli, Virgilio P; Cogo, Paola E

    2014-10-01

    Surfactant protein C (SP-C) is deemed as the surfactant protein most specifically expressed in type II alveolar epithelial cells and plays an important role in surfactant function. SP-C turnover in humans and its meaning in the clinical context have never been approached. In this study, we used mass spectrometry to investigate SP-C turnover in humans. We studied four infants and eight adults requiring mechanical ventilation. All patients had no lung disease. Patients received a 24-h continuous infusion of (13)C-leucine as precursor of SP-C, and serial tracheal aspirates and plasma samples were obtained every 6 h till 48 h. SP-C was isolated from tracheal aspirates by sorbent-phase chromatography. (13)C-leucine SP-C enrichment could be successfully measured in three infant and in four adult samples by using mass spectrometry coupled with a gas chromatographer. Median SP-C fractional synthesis rate, secretion time, and peak time were 15.7 (14.1-27.5)%/day, 6.0 (4.7-11.5) h, and 24 (20-27) h. In conclusion, this study shows that it is feasible to accurately determine SP-C turnover in humans by stable isotopes. PMID:25182966

  16. Accuracy of some routine method used in clinical chemistry as judged by isotope dilution-mass spectrometry

    SciTech Connect

    Bjoerkhem, I.; Bergman, A.; Falk, O.; Kallner, A.; Lantto, O.; Svensson, L.; Akerloef, E.; Blomstrand, R.

    1981-05-01

    Serum from patients was pooled, filtered, dispensed, and frozen. This pooled specimen was used for accuracy control in 64 participating laboratories in Sweden. Mean values (state-of-the-art values) were obtained for creatinine, cholesterol, glucose, urea, uric acid, and cortisol. These values were compared with values obtained with highly accurate reference methods based on isotope dilution-mass spectrometry. Differences were marked in the case of determination of creatinine and cortisol. Concerning the other components, the differences between the state-of-the-art value and the values obtained with the reference methods were negligible. Moreover, the glucose oxidase and the oxime methods for determination of glucose and urea were found to give significantly lower values than the hexokinase and urease methods, respectively. Researchers conclude that methods with a higher degree of accuracy are required for routine determination of creatinine and cortisol.

  17. Application of Screening Experimental Designs to Assess Chromatographic Isotope Effect upon Isotope-Coded Derivatization for Quantitative Liquid Chromatography–Mass Spectrometry

    PubMed Central

    2015-01-01

    Isotope effect may cause partial chromatographic separation of labeled (heavy) and unlabeled (light) isotopologue pairs. Together with a simultaneous matrix effect, this could lead to unacceptable accuracy in quantitative liquid chromatography–mass spectrometry assays, especially when electrospray ionization is used. Four biologically relevant reactive aldehydes (acrolein, malondialdehyde, 4-hydroxy-2-nonenal, and 4-oxo-2-nonenal) were derivatized with light or heavy (d3-, 13C6-, 15N2-, or 15N4-labeled) 2,4-dinitrophenylhydrazine and used as model compounds to evaluate chromatographic isotope effects. For comprehensive assessment of retention time differences between light/heavy pairs under various gradient reversed-phase liquid chromatography conditions, major chromatographic parameters (stationary phase, mobile phase pH, temperature, organic solvent, and gradient slope) and different isotope labelings were addressed by multiple-factor screening using experimental designs that included both asymmetrical (Addelman) and Plackett–Burman schemes followed by statistical evaluations. Results confirmed that the most effective approach to avoid chromatographic isotope effect is the use of 15N or 13C labeling instead of deuterium labeling, while chromatographic parameters had no general influence. Comparison of the alternate isotope-coded derivatization assay (AIDA) using deuterium versus 15N labeling gave unacceptable differences (>15%) upon quantifying some of the model aldehydes from biological matrixes. On the basis of our results, we recommend the modification of the AIDA protocol by replacing d3-2,4-dinitrophenylhydrazine with 15N- or 13C-labeled derivatizing reagent to avoid possible unfavorable consequences of chromatographic isotope effects. PMID:24922593

  18. Protein Structure-Function Correlation in Living Human Red Blood Cells Probed by Isotope Exchange-based Mass Spectrometry.

    PubMed

    Narayanan, Sreekala; Mitra, Gopa; Muralidharan, Monita; Mathew, Boby; Mandal, Amit K

    2015-12-01

    To gain insight into the underlying mechanisms of various biological events, it is important to study the structure-function correlation of proteins within cells. Structural probes used in spectroscopic tools to investigate protein conformation are similar across all proteins. Therefore, structural studies are restricted to purified proteins in vitro and these findings are extrapolated in cells to correlate their functions in vivo. However, due to cellular complexity, in vivo and in vitro environments are radically different. Here, we show a novel way to monitor the structural transition of human hemoglobin upon oxygen binding in living red blood cells (RBCs), using hydrogen/deuterium exchange-based mass spectrometry (H/DX-MS). Exploiting permeability of D2O across cell membrane, the isotope exchange of polypeptide backbone amide hydrogens of hemoglobin was carried out inside RBCs and monitored using matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS). To explore the conformational transition associated with oxygenation of hemoglobin in vivo, the isotope exchange kinetics was simplified using the method of initial rates. RBC might be considered as an in vivo system of pure hemoglobin. Thus, as a proof-of-concept, the observed results were correlated with structural transition of hemoglobin associated with its function established in vitro. This is the first report on structural changes of a protein upon ligand binding in its endogenous environment. The proposed method might be applicable to proteins in their native state, irrespective of location, concentration, and size. The present in-cell approach opens a new avenue to unravel a plethora of biological processes like ligand binding, folding, and post-translational modification of proteins in living cells. PMID:26531244

  19. Isotope pattern deconvolution for peptide mass spectrometry by non-negative least squares/least absolute deviation template matching

    PubMed Central

    2012-01-01

    Background The robust identification of isotope patterns originating from peptides being analyzed through mass spectrometry (MS) is often significantly hampered by noise artifacts and the interference of overlapping patterns arising e.g. from post-translational modifications. As the classification of the recorded data points into either ‘noise’ or ‘signal’ lies at the very root of essentially every proteomic application, the quality of the automated processing of mass spectra can significantly influence the way the data might be interpreted within a given biological context. Results We propose non-negative least squares/non-negative least absolute deviation regression to fit a raw spectrum by templates imitating isotope patterns. In a carefully designed validation scheme, we show that the method exhibits excellent performance in pattern picking. It is demonstrated that the method is able to disentangle complicated overlaps of patterns. Conclusions We find that regularization is not necessary to prevent overfitting and that thresholding is an effective and user-friendly way to perform feature selection. The proposed method avoids problems inherent in regularization-based approaches, comes with a set of well-interpretable parameters whose default configuration is shown to generalize well without the need for fine-tuning, and is applicable to spectra of different platforms. The R package IPPD implements the method and is available from the Bioconductor platform (http://bioconductor.fhcrc.org/help/bioc-views/devel/bioc/html/IPPD.html). PMID:23137144

  20. Discovery of Histone Modification Crosstalk Networks by Stable Isotope Labeling of Amino Acids in Cell Culture Mass Spectrometry (SILAC MS)*

    PubMed Central

    Guan, Xiaoyan; Rastogi, Neha; Parthun, Mark R.; Freitas, Michael A.

    2013-01-01

    In this paper we describe an approach that combines stable isotope labeling of amino acids in cells culture, high mass accuracy liquid chromatography tandem mass spectrometry and a novel data analysis approach to accurately determine relative peptide post-translational modification levels. This paper describes the application of this approach to the discovery of novel histone modification crosstalk networks in Saccharomyces cerevisiae. Yeast histone mutants were generated to mimic the presence/absence of 44 well-known modifications on core histones H2A, H2B, H3, and H4. In each mutant strain the relative change in H3 K79 methylation and H3 K56 acetylation were determined using stable isotope labeling of amino acids in cells culture. This approach showed relative changes in H3 K79 methylation and H3 K56 acetylation that are consistent with known histone crosstalk networks. More importantly, this study revealed additional histone modification sites that affect H3 K79 methylation and H3 K56 acetylation. PMID:23592332

  1. Simultaneous Detection of Androgen and Estrogen Abuse in Breeding Animals by Gas Chromatography-Mass Spectrometry/Combustion/Isotope Ratio Mass Spectrometry (GC-MS/C/IRMS) Evaluated against Alternative Methods.

    PubMed

    Janssens, Geert; Mangelinckx, Sven; Courtheyn, Dirk; De Kimpe, Norbert; Matthijs, Bert; Le Bizec, Bruno

    2015-09-01

    The administration of synthetic homologues of naturally occurring steroids can be demonstrated by measuring (13)C/(12)C isotopic ratios of their urinary metabolites. Gas chromatography-mass spectrometry/combustion/isotope ratio mass spectrometry (GC-MS/C/IRMS) was used in this study to appraise in a global approach isotopic deviations of two 17?-testosterone metabolites (17?-testosterone and etiocholanolone) and one 17?-estradiol metabolite (17?-estradiol) together with those of 5-androstene-3?,17?-diol as endogenous reference compound (ERC). Intermediate precisions of 0.35‰, 1.05‰, 0.35‰, and 0.21‰, respectively, were observed (n = 8). To assess the performance of the analytical method, a bull and a heifer were treated with 17?-testosterone propionate and 17?-estradiol-3-benzoate. The sensitivity of the method permitted the demonstration of 17?-estradiol treatment up to 24 days. For 17?-testosterone treatment, the detection windows were 3 days and 24 days for the bull and the heifer, respectively. The capability of GC-MS/C/IRMS to demonstrate natural steroid abuse for urinary steroids was eventually compared to those of mass spectrometry (LC-MS/MS) when measuring intact steroid esters in blood and hair. PMID:26271751

  2. BIOLOGICAL ANALYSIS Mass Spectrometry

    E-print Network

    Painter, Kevin

    Single Crystal X-ray Diffractometry Mass Spectrometry Elemental Analysis (CHN) Other Analytical Methods chamber with Near field scanner Superconductor Chamber Microwave Network Analysers OPTICAL DIAGNOSTICS

  3. DETERMINATION OF 5-METHYLTETRAHYDROFOLIC ACID IN HUMAN SERUM BY STABLE-ISOTOPE DILUTION HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY-MASS SPECTROMETRY

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This report describes a stable isotope liquid chromatography-mass spectrometry (LC-MS) method that was developed for the quantitative determination of 5-methyltetrahydrofolic acid (5-MTHFA) and folic acid in a variety of citrus juices. Folates were extracted from juices and the polyglutamyl side ch...

  4. Measurement of Niacin in a Variety of Food Samples by High Performance Liquid Chromatography-Stable Isotope Dilution Mass Spectrometry (AOAC Annual Meeting, Minneapolis, MN, Sept. 2006)

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The availability of deuterium-labeled nicotinic acid makes stable isotope dilution mass spectrometry (SIDMS) coupled with liquid chromatography (LC) an attractive option for the determination of the water-soluble B-vitamin, niacin, in food samples. We have developed a method based on AOAC Peer-Verif...

  5. Measurement of Niacin in a Variety of Food Samples by High Performance Liquid Chromatography-Stable Isotope Dilution Mass Spectrometry (Experimental Biology, April, 2007, Washington, D.C.)

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The availability of deuterium-labeled nicotinic acid makes stable isotope dilution mass spectrometry (SIDMS) coupled with liquid chromatography (LC) an attractive option for the determination of the water-soluble B-vitamin, niacin, in food samples. We have developed a method based on AOAC Peer-Verif...

  6. 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 selected pesticides in soya beans at appropriate uncertainty levels, making it suitable for the characterization of candidate reference materials. PMID:25770614

  7. Gas Chromatography -Mass Spectrometry

    E-print Network

    Nizkorodov, Sergey

    GCMS - 1 Gas Chromatography - Mass Spectrometry GC-MS ANALYSIS OF ETHANOL AND BENZENE IN GASOLINE Last updated: June 17, 2014 #12;GCMS - 2 Gas Chromatography - Mass Spectrometry GC-MS ANALYSIS). The goal of this experiment is to separate the components in a sample of gasoline using Gas Chromatography

  8. Quantification of Cr(VI) in soil samples from a contaminated area in northern Italy by isotope dilution mass spectrometry.

    PubMed

    Guidotti, Laura; Abad, Silvia Queipo; Rodríguez-González, Pablo; Alonso, J Ignacio García; Beone, Gian Maria

    2015-11-01

    The aims of the work were to detect and quantify hexavalent chromium in 14 soil samples from an area in Lombardia (northern Italy) contaminated by two polluted water plumes. Cr(VI) was extracted from the solid samples by applying focused microwaves in an alkaline medium after Cr(III) complexation with EDTA. Cr(VI) was reduced to Cr(III) when previously reported extraction conditions for the analysis of certified reference materials were used, and Cr(VI) could not be reliably quantified in the soil samples. The influence of organic matter and iron contents in the samples on the reduction of Cr(VI) was subsequently studied using a new set of soil samples with different iron and organic matter concentrations. Isotope dilution mass spectrometry (IDMS) measured two different enriched stable isotopes of Cr (54 and 53) to evaluate the reduction extent of hexavalent chromium during the analytical procedure. The extraction conditions were optimized to obtain the lowest amount of Cr(VI) reduction and quantify Cr(VI) in the polluted soil samples from Lombardia. PMID:26141979

  9. Determination of technetium-99 in aqueous samples by isotope dilution inductively coupled plasma-mass spectrometry

    SciTech Connect

    Beals, D.M.

    1992-01-01

    An isotope dilution/inductively coupled plasma mass spectrometric method (ID/ICP-MS) for measuring the concentration of technetium-99 in aqueous samples was developed at the Savannah River Technology Center (SRTC). The procedure is faster than radiometric techniques, is also less subject to interferences, and has equal or better detection limits. It is currently being used to measure the concentration of {sup 99}Tc in samples of Savannah River water collected in the vicinity of the Savannah River Site. In this method, one liter samples of water are spiked with {sup 97}Tc. After equilibration, the technetium is extracted from the sample with a chromatographic resin. Interfering elements, molybdenum and ruthenium, are either not retained by the resin or are washed off with dilute nitric acid. The technetium is then eluted with more concentrated nitric acid, and the {sup 99}Tc/{sup 97}Tc ratio in the eluant is measured with an ICP-MS. The {sup 99}Tc concentration in the original sample is calculated from the {sup 99}Tc/{sup 97}Tc ratio. The chemical recovery of the extraction procedure is greater than 90%. The detection limit of the instrument, taken as three times the background counts at m/z = 99, is 0.6 part per trillion (ppt). The detection limit of the procedure, taken as three times the standard deviation of several reagent blank analyses, is 0.33 pCi/L.

  10. Determination of technetium-99 in aqueous samples by isotope dilution inductively coupled plasma-mass spectrometry

    SciTech Connect

    Beals, D.M.

    1992-09-01

    An isotope dilution/inductively coupled plasma mass spectrometric method (ID/ICP-MS) for measuring the concentration of technetium-99 in aqueous samples was developed at the Savannah River Technology Center (SRTC). The procedure is faster than radiometric techniques, is also less subject to interferences, and has equal or better detection limits. It is currently being used to measure the concentration of {sup 99}Tc in samples of Savannah River water collected in the vicinity of the Savannah River Site. In this method, one liter samples of water are spiked with {sup 97}Tc. After equilibration, the technetium is extracted from the sample with a chromatographic resin. Interfering elements, molybdenum and ruthenium, are either not retained by the resin or are washed off with dilute nitric acid. The technetium is then eluted with more concentrated nitric acid, and the {sup 99}Tc/{sup 97}Tc ratio in the eluant is measured with an ICP-MS. The {sup 99}Tc concentration in the original sample is calculated from the {sup 99}Tc/{sup 97}Tc ratio. The chemical recovery of the extraction procedure is greater than 90%. The detection limit of the instrument, taken as three times the background counts at m/z = 99, is 0.6 part per trillion (ppt). The detection limit of the procedure, taken as three times the standard deviation of several reagent blank analyses, is 0.33 pCi/L.

  11. Pathway of diethyl phthalate photolysis in sea-water determined by gas chromatography-mass spectrometry and compound-specific isotope analysis.

    PubMed

    Peng, Xuewei; Feng, Lijuan; Li, Xianguo

    2013-01-01

    The degradation mechanism of diethyl phthalate (DEP) in natural seawater under UV irradiation was investigated using a combination of intermediates detection and determination of stable carbon isotopic fractionation. Typical intermediates identified with gas chromatography-mass spectrometry (GC-MS) were mono-ethyl phthalate (MEP) and phthalic anhydride. Stable carbon isotope signature was determined by gas chromatography coupled with isotope ratio mass spectrometry through a combustion interface (GC-C-IRMS). A profound (13)C enrichment, with a ?(13)C isotope shift of 12.3±0.3‰ (f=0.09) in residual DEP molecule, was clearly an indicator to its photolysis. The reactive position isotope enrichment factor (?(reactive position)) and apparent kinetic isotope effects (AKIE) were -35.25±2.26‰ and 1.075, respectively, indicating that the initial reaction step was cleavage of a CO bond in DEP photolysis. Based on these observations, a degradation pathway was proposed. First, a CO bond in DEP molecule was broken to form MEP. Then, MEP was further degraded to phthalic anhydride. Our work demonstrates that compound-specific isotope analysis (CSIA), when combined with intermediates analysis, is a reliable measure to deduce the mechanism of DEP photolysis. This approach might be extended as a reference for mechanism investigation in complicated environment systems. PMID:22883110

  12. Stable Chlorine Isotopes and Elemental Chlorine by Thermal Ionization Mass Spectrometry and Ion Chromatography; Martian Meteorites, Carbonaceous Chondrites and Standard Rocks

    NASA Technical Reports Server (NTRS)

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

    2011-01-01

    Recently significantly large mass fractionation of stable chlorine isotopes has been reported for terrestrial and lunar samples [1,2]. In addition, in view of possible early solar system processes [3] and also potential perchlorate-related fluid/microbial activities on the Martian surface [4,5], a large chlorine isotopic fractionation might be expected for some types of planetary materials. Due to analytical difficulties of isotopic and elemental analyses, however, current chlorine analyses for planetary materials are controversial among different laboratories, particularly between IRMS (gas source mass spectrometry) and TIMS (Thermal Ionization Mass Spectrometry) groups [i.e. 1,6,7] for isotopic analyses, as well as between those doing pyrohydrolysis and other groups [i.e. 6,8]. Additional careful investigations of Cl isotope and elemental abundances are required to confirm real chlorine isotope and elemental variations for planetary materials. We have developed a TIMS technique combined with HF-leaching/ion chromatography at NASA JSC that is applicable to analysis of small amounts of meteoritic and planetary materials. We present here results for several standard rocks and meteorites, including Martian meteorites.

  13. Carbon Isotope Measurements of Experimentally-Derived Hydrothermal Mineral-Catalyzed Organic Products by Pyrolysis-Isotope Ratio Mass Spectrometry

    NASA Technical Reports Server (NTRS)

    Socki, Richard A.; Fu, Qi; Niles, Paul B.

    2011-01-01

    We report results of experiments to measure the C isotope composition of mineral catalyzed organic compounds derived from high temperature and high pressure synthesis. These experiments make use of an innovative pyrolysis technique designed to extract and measure C isotopes. To date, our experiments have focused on the pyrolysis and C isotope ratio measurements of low-molecular weight intermediary hydrocarbons (organic acids and alcohols) and serve as a proof of concept for making C and H isotope measurements on more complicated mixtures of solid-phase hydrocarbons and intermediary products produced during high temperature and high pressure synthesis on mineral-catalyzed surfaces. The impetus for this work stems from recently reported observations of methane detected within the Martian atmosphere [1-4], coupled with evidence showing extensive water-rock interaction during Martian history [5-7]. Methane production on Mars could be the result of synthesis by mineral surface-catalyzed reduction of CO2 and/or CO by Fischer-Tropsch Type (FTT) reactions during serpentization reactions [8,9]. Others have conducted experimental studies to show that FTT reactions are plausible mechanisms for low-molecular weight hydrocarbon formation in hydrothermal systems at mid-ocean ridges [10-12]. Further, recent experiments by Fu et al. [13] focus on examining detailed C isotope measurements of hydrocarbons produced by surface-catalyzed mineral reactions. Work described in this paper details the experimental techniques used to measure intermediary organic reaction products (alcohols and organic acids).

  14. Nicotine, acetanilide and urea multi-level2H-,13C- and15N-abundance reference materials for continuous-flow isotope ratio mass spectrometry

    USGS Publications Warehouse

    Schimmelmann, A.; Albertino, A.; Sauer, P.E.; Qi, H.; Molinie, R.; Mesnard, F.

    2009-01-01

    Accurate determinations of stable isotope ratios require a calibration using at least two reference materials with different isotopic compositions to anchor the isotopic scale and compensate for differences in machine slope. Ideally, the S values of these reference materials should bracket the isotopic range of samples with unknown S values. While the practice of analyzing two isotopically distinct reference materials is common for water (VSMOW-SLAP) and carbonates (NBS 19 and L-SVEC), the lack of widely available organic reference materials with distinct isotopic composition has hindered the practice when analyzing organic materials by elemental analysis/isotope ratio mass spectrometry (EA-IRMS). At present only L-glutamic acids USGS40 and USGS41 satisfy these requirements for ??13C and ??13N, with the limitation that L-glutamic acid is not suitable for analysis by gas chromatography (GC). We describe the development and quality testing of (i) four nicotine laboratory reference materials for on-line (i.e. continuous flow) hydrogen reductive gas chromatography-isotope ratio mass-spectrometry (GC-IRMS), (ii) five nicotines for oxidative C, N gas chromatography-combustion-isotope ratio mass-spectrometry (GC-C-IRMS, or GC-IRMS), and (iii) also three acetanilide and three urea reference materials for on-line oxidative EA-IRMS for C and N. Isotopic off-line calibration against international stable isotope measurement standards at Indiana University adhered to the 'principle of identical treatment'. The new reference materials cover the following isotopic ranges: ??2Hnicotine -162 to -45%o, ??13Cnicotine -30.05 to +7.72%, ?? 15Nnicotine -6.03 to +33.62%; ??15N acetanilide +1-18 to +40.57%; ??13Curea -34.13 to +11.71%, ??15Nurea +0.26 to +40.61% (recommended ?? values refer to calibration with NBS 19, L-SVEC, IAEA-N-1, and IAEA-N-2). Nicotines fill a gap as the first organic nitrogen stable isotope reference materials for GC-IRMS that are available with different ??13N values. Comparative ??13C and ??15N on-line EA-IRMS data from 14 volunteering laboratories document the usefulness and reliability of acetanilides and ureas as EA-IRMS reference materials.

  15. Isotope-Encoded Carboxyl Group Footprinting for Mass Spectrometry-Based Protein Conformational Studies

    NASA Astrophysics Data System (ADS)

    Zhang, Hao; Liu, Haijun; Blankenship, Robert E.; Gross, Michael L.

    2015-09-01

    We report an isotope-encoding method coupled with carboxyl-group footprinting to monitor protein conformational changes. The carboxyl groups of aspartic/glutamic acids and of the C-terminus of proteins can serve as reporters for protein conformational changes when labeled with glycine ethyl ester (GEE) mediated by carbodiimide. In the new development, isotope-encoded "heavy" and "light" GEE are used to label separately the two states of the orange carotenoid protein (OCP) from cyanobacteria. Two samples are mixed (1:1 ratio) and analyzed by a single LC-MS/MS experiment. The differences in labeling extent between the two states are represented by the ratio of the "heavy" and "light" peptides, providing information about protein conformational changes. Combining isotope-encoded MS quantitative analysis and carboxyl-group footprinting reduces the time of MS analysis and improves the sensitivity of GEE and other footprinting.

  16. Isotope-Encoded Carboxyl Group Footprinting for Mass Spectrometry-Based Protein Conformational Studies.

    PubMed

    Zhang, Hao; Liu, Haijun; Blankenship, Robert E; Gross, Michael L

    2016-01-01

    We report an isotope-encoding method coupled with carboxyl-group footprinting to monitor protein conformational changes. The carboxyl groups of aspartic/glutamic acids and of the C-terminus of proteins can serve as reporters for protein conformational changes when labeled with glycine ethyl ester (GEE) mediated by carbodiimide. In the new development, isotope-encoded "heavy" and "light" GEE are used to label separately the two states of the orange carotenoid protein (OCP) from cyanobacteria. Two samples are mixed (1:1 ratio) and analyzed by a single LC-MS/MS experiment. The differences in labeling extent between the two states are represented by the ratio of the "heavy" and "light" peptides, providing information about protein conformational changes. Combining isotope-encoded MS quantitative analysis and carboxyl-group footprinting reduces the time of MS analysis and improves the sensitivity of GEE and other footprinting. Graphical Abstract ?. PMID:26384685

  17. Characterization of candidate reference materials for bone lead via interlaboratory study and double isotope dilution mass spectrometry

    PubMed Central

    Bellis, David J.; Hetter, Katherine M.; Verostek, Mary Frances; Parsons, Patrick J.

    2012-01-01

    Summary Four candidate ground bone reference materials (NYS RMs 05-01 through 04), were produced from lead-dosed bovine and caprine sources, and characterized by interlaboratory study. The consensus value ( X ) and expanded standard uncertainty (UX ) were determined from the robust average and standard deviation of the participants’ data for each NYS RM 05-01 through 04. The values were 1.08 ±0.04, 15.3 ±0.5, 12.4 ±0.5, and 29.9 ±1.1 ?g g?1 Pb, respectively. Youden plots of z-scores showed a statistically significant correlation between the results for pairs of NYS RM 05-02 through 04, indicating common sources of between-laboratory variation affecting reproducibility. NYS RM 05-01 exhibited more random variability affecting repeatability at low concentration. Some participants using electrothermal atomic absorption spectrometry (ETAAS) exhibited a negative bias compared to the all-method consensus value. Other methods used included inductively coupled plasma mass spectrometry (ICP-MS), isotope dilution (ID-) ICP-MS, and ICP atomic (optical) emission spectroscopy (-OES). The NYS RMs 05-01 through 04 were subsequently re-analyzed in house using double ID-ICP-MS to assign certified reference values (C ) and expanded uncertainty (UC ) of 1.09 ± 0.03, 16.1 ± 0.3, 13.2 ± 0.3 and 31.5 ± 0.7, respectively, indicating a low bias in the interlaboratory data. SRM 1486 Bone Meal was analyzed for measurement quality assessment obtaining results in agreement with the certified values within the stated uncertainty. Analysis using a primary reference method based on ID-ICP-MS with full quantification of uncertainty calculated according to ISO guidelines provided traceability to SI units. PMID:23087531

  18. Determination of ultratrace levels of tributyltin in waters by isotope dilution and gas chromatography coupled to tandem mass spectrometry.

    PubMed

    Rodríguez-Cea, Andrés; Rodríguez-González, Pablo; Font Cardona, Nuria; Aranda Mares, José Luís; Ballester Nebot, Salomé; García Alonso, J Ignacio

    2015-12-18

    The current EU legislation lays down the Environmental Quality Standards (EQS) of 45 priority substances in surface water bodies. In particular, the concentration of tributyltin (TBT) must not exceed 0.2ngL(-1) and analytical methodologies with a Limit of Quantification (LOQ) equal or below 0.06ngL(-1) are urged to be developed. This work presents a procedure for the determination of ultratrace levels of TBT in water samples by Isotope Dilution and GC-MS/MS operating in Selected Reaction Monitoring (SRM) mode which meets current EU requirements. The method requires the monitorization of five consecutive transitions (287>175 to 291>179) for the sensitive and selective detection of TBT. The measured isotopic distribution of TBT fragment ions was in agreement with the theoretical values computed by a polynomial expansion algorithm. The combined use of Tandem Mass Spectrometry, a sample volume of 250mL, the preconcentration of 1mL of organic phase to 30?L and an injection volume of 25?L by Programmed Temperature Vaporization provided a LOQ of 0.0426ngL(-1) for TBT (calculated as ten times the standard deviation of nine independent blanks). The recovery for TBT calculated in Milli-Q water at the EQS level was 106.3±4%. A similar procedure was also developed for the quantification of dibutyltin (DBT) and monobutyltin (MBT) in water samples showing satisfactory results. The method was finally implemented in a routine testing laboratory to demonstrate its applicability to real samples obtaining quantitative recoveries for TBT at the EQS level in mineral water, river water and seawater. PMID:26614170

  19. Determination of Mercury Content in a Shallow Firn Core from Summit, Greenland by Isotope Dilution Inductively Coupled Plasma Mass Spectrometry

    NASA Technical Reports Server (NTRS)

    Mann, Jacqueline L.; Long, Stephen E.; Shuman, Christopher A.; Kelly, W. Robert

    2003-01-01

    The total mercury Hg content was determined in 6 cm sections of a near-surface 7 m firn core and in surrounding surface snow from Summit, Greenland (elevation: 3238 m, 72.58 N, 38.53 W) in May 2001 by isotope dilution cold-vapor inductively coupled plasma mass spectrometry (ID-CV-ICP-MS). The focus of this research was to evaluate the capability of the ID-CV-ICPMS technique for measuring trace levels of Hg typical of polar snow and firn. Highly enriched Hg-201 isotopic spike is added to approximately 10 ml melted core and thoroughly mixed. The Hg(+2) in the sample is reduced on line with tin (II) chloride (SnCl2) and the elemental Hg (Hg(0)) vapor pre-concentrated on to gold gauze using a commercial amalgam system. The Hg is then thermally desorbed and introduced into a quadrupole ICP-MS. The blank corrected Hg concentrations determined for all samples ranged from 0.25 ng/L to 1.74 ng/L (ppt) (average 0.59 ng/L plus or minus 0.28 ng/L) and fall within the range of those previously determined by Boutron et al., 1998 (less than or equal to 0.05 ng/L to 2.0 ng/L) for the Summit site. The average blank value was 0.19 ng/L plus or minus 0.045 ng/L (n=6). The Hg values specifically for the firn core range from 0.25 ng/L to 0.87 ng/L (average 0.51 ng/L plus or minus 0.13 ng/L) and show both values declining with time and larger variability in concentration in the top 1.8 m.

  20. A 10-fold improvement in the precision of boron isotopic analysis by negative thermal ionization mass spectrometry.

    PubMed

    Shen, Jason Jiun-San; You, Chen-Feng

    2003-05-01

    Boron isotopes are potentially very important to cosmochemistry, geochemistry, and paleoceanography. However, the application has been hampered by the large sample required for positive thermal ionization mass spectrometry (PTIMS), and high mass fractionation for negative-TIMS (NTIMS). Running as BO(2)(-), NTIMS is very sensitive and requires only nanogram sized samples, but it has rather poor precision (approximately 0.7-2.0 per thousand) as a result of the larger mass fractionation associated with the relatively light ion. In contrast, running as the much heavier molecule of Cs(2)BO(2)(+), PTIMS usually achieves better precision around 0.1-0.4 per thousand. Moreover, there is a consistent 10 per thousand offset in the (11)B/(10)B ratio for NIST SRM 951 standard boric acid between the NTIMS and the certified value, but the cause of this offset is unclear. In this paper, we have adapted a technique we developed earlier to measure the (138)La/(139)La using LaO(+) (1) to improve the NTIMS technique for BO(2). We were able to correct for instrumental fractionation by measuring BO(2)(-) species not only at masses of 42 and 43, but also at 45, which enabled us to normalize (45)BO(2)/(43)BO(2) to an empirical (18)O/(16)O value. We found that both I(45)/I(42) = ((11)B(16)O(18)O/(10)B(16)O(16)O) and (I(43)/I(42))(C) = ((11)B(16)O(16)O/(10)B(16)O(16)O) vary linearly with (I(45)/I(43))(C) x 0.5 = ((11)B(16)O(18)O/(11)B(16)O(16)O) x 0.5 = (18)O/(16)O. In addition, different activators and different chemical forms of B yield different slopes for the fractionation lines. After normalizing (11)B(16)O(18)O/(11)B(16)O(16)O x 0.5 to a fixed (18)O/(16)O value, we obtained a mean (11)B/(10)B value of NIST SRM 951 that matches the NIST certified value at 4.0430 +/- 0.0015 (+/-0.36 per thousand, n = 11). As a result, our technique can achieve precision and accuracy comparable to that of PTIMS with only 1 per thousand of the sample required. This new NTIMS technique for B isotopes is critical to the studies of early solids in the solar system and individual foraminifera in sediments that require both high sensitivity and precision. PMID:12720329

  1. 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

  2. Determining mycotoxins in baby foods and animal feeds using stable isotope dilution and liquid chromatography tandem mass spectrometry.

    PubMed

    Zhang, Kai; Wong, Jon W; Krynitsky, Alexander J; Trucksess, Mary W

    2014-09-10

    We developed a stable isotope dilution assay with liquid chromatography tandem mass spectrometry (LC-MS/MS) to determine multiple mycotoxins in baby foods and animal feeds. Samples were fortified with [(13)C]-uniformly labeled mycotoxins as internal standards ([(13)C]-IS) and prepared by solvent extraction (50% acetonitrile in water) and filtration, followed by LC-MS/MS analysis. Mycotoxins in each sample were quantitated with the corresponding [(13)C]-IS. In general, recoveries of aflatoxins (2-100 ng/g), deoxynivalenol, fumonisins (50-2000 ng/g), ochratoxin A (20-1000 ng/kg), T-2 toxin, and zearalenone (40-2000 ng/g) in tested matrices (grain/rice/oatmeal-based formula, animal feed, dry cat/dog food) ranged from 70 to 120% with relative standard deviations (RSDs) <20%. The method provides sufficient selectivity, sensitivity, accuracy, and reproducibility to screen for aflatoxins at ng/g concentrations and deoxynivalenol and fumonisins at low ?g/g concentrations in baby foods and animal feeds, without using conventional standard addition or matrix-matched calibration standards to correct for matrix effects. PMID:25153173

  3. Determination of rhizosphere 13C pulse signals in soil thin sections by laser ablation isotope ratio mass spectrometry.

    PubMed

    Bruneau, Patricia M C; Ostle, Nick; Davidson, Donald A; Grieve, Ian C; Fallick, Anthony E

    2002-01-01

    In grassland ecosystems, soil animals act as key soil engineers and architects. The diversity of soil animals is also a regulator of ecosystem carbon flow. However, our understanding of the link between soil animals, carbon fluxes and soil physical organisation remains poor. An integrated approach based on soil micromorphology and laser ablation stable isotope ratio mass spectrometry (LA-IRMS) was developed to provide spatially distributed data of pulse-derived (13)C tracer from roots in the soil environment. This paper describes the development and testing of a LA-IRMS (13)C/(12)C analytical method on soil thin sections as a means to determine the fate of root carbon derived from photosynthesis into soil. Results from this work demonstrated (1) that micro-scale delta(13)C (per thousand) analysis could be made on targeted features located within a soil thin section and (2) that LA-IRMS delta(13)C (per thousand) measurements made on samples obtained from (13)CO(2) pulse labelled plant-soil blocks confirmed the presence of recent photosynthates in the rhizosphere (1 and 4 weeks post-pulse). PMID:12442294

  4. Analysis of nitromethane from samples exposed in vitro to chloropicrin by stable isotope dilution headspace gas chromatography with mass spectrometry.

    PubMed

    Halme, Mia; Pesonen, Maija; Grandell, Toni; Kuula, Matti; Pasanen, Markku; Vähäkangas, Kirsi; Vanninen, Paula

    2015-10-01

    Chloropicrin (trichloronitromethane) is a widely used soil fumigant and an old chemical warfare agent. The metabolism of chloropicrin is not well known in mammals but nitromethane has been shown to be one of its main metabolites. Here, a fast and simple headspace gas chromatography with mass spectrometry method was applied for the measurement of nitromethane from aqueous samples. The analytical method was validated using stable isotope labeled internal standard and a small sample volume of 260 ?L. No conventional sample preparation steps were needed. The method was accurate (relative standard deviations ?1.5%) and linear (R(2) = 0.9996) within the concentration range of 0.1-6.0 ?g/mL. This method was used to measure nitromethane in in vitro incubations with human and pig liver cell fractions containing enzymes for xenobiotic metabolism, exposed to chloropicrin. The results indicate that the presence of glutathione is necessary for the formation of nitromethane from chloropicrin. Also, nitromethane was formed mostly in liver cytosol fractions, but not in microsomal fractions after the incubation with chloropicrin. Our results suggest that although nitromethane is not the unequivocal biomarker of chloropicrin exposure, this method could be applied for screening the elevated levels in humans after chloropicrin exposure. PMID:26255649

  5. Spatially resolved ?13C 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 ?m 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.

  6. Stable isotope imaging of biological samples with high resolution secondary ion mass spectrometry and complementary techniques.

    PubMed

    Jiang, H; Favaro, E; Goulbourne, C N; Rakowska, P D; Hughes, G M; Ryadnov, M G; Fong, L G; Young, S G; Ferguson, D J P; Harris, A L; Grovenor, C R M

    2014-07-01

    Stable isotopes are ideal labels for studying biological processes because they have little or no effect on the biochemical properties of target molecules. The NanoSIMS is a tool that can image the distribution of stable isotope labels with up to 50 nm spatial resolution and with good quantitation. This combination of features has enabled several groups to undertake significant experiments on biological problems in the last decade. Combining the NanoSIMS with other imaging techniques also enables us to obtain not only chemical information but also the structural information needed to understand biological processes. This article describes the methodologies that we have developed to correlate atomic force microscopy and backscattered electron imaging with NanoSIMS experiments to illustrate the imaging of stable isotopes at molecular, cellular, and tissue scales. Our studies make it possible to address 3 biological problems: (1) the interaction of antimicrobial peptides with membranes; (2) glutamine metabolism in cancer cells; and (3) lipoprotein interactions in different tissues. PMID:24556558

  7. Carbon isotope ratio analysis of organic moieties from fossil mummified wood: establishing optimum conditions for off-line pyrolysis extraction using gas chromatography/mass spectrometry.

    PubMed

    Poole, Imogen; van Bergen, Pim F

    2002-01-01

    Mummified fossil wood was studied using off-line pyrolysis-gas chromatography/mass spectrometry to reveal detailed insights into the pyrolysis conditions that are needed to obtain simultaneously sufficient amounts of both cellulose and lignin markers for stable carbon isotope analyses. The off-line pyrolysis was applied at a range of temperatures (200, 250 and 300 degrees C) and times (1 and 2 h) to determine the optimum temperature and time that yielded the highest quantity of true markers for lignin and cellulose. Increasing the time from 1 to 2 h had no effect whereas increasing the temperature led to large differences. The products released during the low-temperature pyrolysis were mostly related to thermally labile moieties. Only at 300 degrees C were sufficient amounts of products released that represent true cellulose and lignin building blocks and which could be studied using gas chromatography/combustion isotope ratio mass spectrometry. PMID:12362390

  8. Advances in low level uranium and plutonium isotope mass spectrometry using multiple ion counting and filament carburization

    NASA Astrophysics Data System (ADS)

    Richter, S.; Jakopic, R.; Kuehn, H.; Alonso, A.; Aregbe, Y.

    2008-12-01

    After upgrading IRMM's mass spectrometric capabilities for certification measurements for uranium and plutonium using large sample sizes during the previous years, in 2006-2007 we focused on necessary improvements in the area of low-level isotopic analyses for uranium and plutonium. This project was driven firstly by the need for reliable verification measurements for the Nuclear Signatures Measurement Evaluation Programme (NUSIMEP) samples at IRMM, secondly by the need for verification measurements on single uranium oxide reference particles and thirdly by the request from the IAEA's Safeguards Analytical Laboratory (SAL) to provide assistance for this type of analyses through the EC support programme. Improving low-level isotope mass spectrometry for uranium and plutonium at IRMM consisted of three steps. First a new thermal ionization mass spectrometer was acquired in order to have an instrument which can be used for peak-jumping measurements in ion counting mode, and which can be subsequently upgraded with a "Multiple Ion Counting" (MIC) system. This detector system allows the simultaneous detection of up to seven small ion beams with currents of 10-19 - 10-14 Ampere in ion counting mode, corresponding to count rates of 1-60.000 counts per second. As a result of test measurements with the MIC system it turned out that static measurements using the MIC system with a sample-versus-standard type external calibration can be associated with uncertainties even higher than in peak-jumping mode. The second step of improvement to tackle this situation was to implement the principle of "multi-dynamic" measurements for both uranium and plutonium measurements. This "multi- dynamic" measurement procedure provides an internal calibration of the MIC system and therefore circumvents the need for complicated inter-calibration routines. As a third step, a filament carburization procedure was implemented by which the ionization efficiencies for uranium and plutonium were improved by a factor of 3 and 10, respectively. Results for measurements performed on samples of previous NUSIMEP campaigns will be shown in comparison to results from various techniques employed by participating laboratories.

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

    As metagenomics increases our insight into microbial community diversity and metabolic potential, new approaches are required to determine the biogeochemical expression of this potential within ecosystems. Because stable isotopic analysis of the major bioactive elements (C, N) has been used historically to map flows of substrates and energy among macroscopic food webs, similar principles may apply to microbes. To address this challenge, we have developed a new analytical approach called Protein Stable Isotope Fingerprinting (P-SIF). P-SIF generates natural stable isotopic fingerprints of microbial individual or community proteomes. The main advantage of P-SIF is the potential to bridge the gap between diversity and function, thereby providing a window into the "black box" of environmental microbiology and helping to decipher the roles of uncultivated species. Our method implements a three-way, orthogonal scheme to separate mixtures of whole proteins into subfractions dominated by single or closely-related proteins. Protein extracts first are isoelectrically focused in a gel-free technique that yields 12 fractions separated over a gradient of pH 3-10. Each fraction then is separated by size-exclusion chromatography into 20 pools, ranging from >100kD to ~10kD. Finally, each of these pools is subjected to HPLC and collected in 40 time-slices based on protein hydrophobicity. Theoretical calculation reveals that the true chromatographic resolution of the total scheme is 5000, somewhat less than the 9600 resulting fractions. High-yielding fractions are subjected to ?13C analysis by spooling-wire microcombustion irMS (SWiM-irMS) optimized for samples containing 1-5 nmol carbon. Here we will present the method, results for a variety of pure cultures, and preliminary data for a sample of mixed environmental proteins. The data show the promise of this method for unraveling the metabolic complexity hidden within microbial communities.

  10. Metabolomics relative quantitation with mass spectrometry using chemical derivatization and isotope labeling

    DOE PAGESBeta

    O'Maille, Grace; Go, Eden P.; Hoang, Linh; Want, Elizabeth J.; Smith, Colin; O'Maille, Paul; NordstrÖm, Anders; Morita, Hirotoshi; Qin, Chuan; Uritboonthai, Wilasinee; et al

    2008-01-01

    Comprehensive detection and quantitation of metabolites from a biological source constitute the major challenges of current metabolomics research. Two chemical derivatization methodologies, butylation and amination, were applied to human serum for ionization enhancement of a broad spectrum of metabolite classes, including steroids and amino acids. LC-ESI-MS analysis of the derivatized serum samples provided a significant signal elevation across the total ion chromatogram to over a 100-fold increase in ionization efficiency. It was also demonstrated that derivatization combined with isotopically labeled reagents facilitated the relative quantitation of derivatized metabolites from individual as well as pooled samples.

  11. Stable isotope gas chromatography-tandem mass spectrometry determination of aminoethylcysteine ketimine decarboxylated dimer in biological samples.

    PubMed

    Tsikas, Dimitrios; Evans, Christopher E; Denton, Travis T; Mitschke, Anja; Gutzki, Frank-Mathias; Pinto, John T; Khomenko, Tetyana; Szabo, Sandor; Cooper, Arthur J L

    2012-11-01

    Aminoethylcysteine ketimine decarboxylated dimer (AECK-DD; systematic name: 1,2-3,4-5,6-7,8-octahydro-1,8a-diaza-4,6-dithiafluoren-9(8aH)-one) is a previously described metabolite of cysteamine that has been reported to be present in mammalian brain, urine, plasma, and cells in culture and vegetables and to possess potent antioxidative properties. Here, we describe a stable isotope gas chromatography-tandem mass spectrometry (GC-MS/MS) method for specific and sensitive determination of AECK-DD in biological samples. (13)C(2)-labeled AECK-DD was synthesized and used as the internal standard. Derivatization was carried out by N-pentafluorobenzylation with pentafluorobenzyl bromide in acetonitrile. Quantification was performed by selected reaction monitoring of the mass transitions m/z 328 to 268 for AECK-DD and m/z 330 to 270 for [(13)C(2)]AECK-DD in the electron capture negative ion chemical ionization mode. The procedure was systematically validated for human plasma and urine samples. AECK-DD was not detectable in human plasma above approximately 4nM but was present in urine samples of healthy humans at a maximal concentration of 46nM. AECK-DD was detectable in rat brain at very low levels of approximately 8pmol/g wet weight. Higher levels of AECK-DD were detected in mouse brain (?1nmol/g wet weight). Among nine dietary vegetables evaluated, only shallots were found to contain trace amounts of AECK-DD (?6.8pmol/g fresh tissue). PMID:22858756

  12. Comparison of secondary ion mass spectrometry and micromilling/continuous flow isotope ratio mass spectrometry techniques used to acquire intra-otolith delta18O values of wild Atlantic salmon (Salmo salar).

    PubMed

    Hanson, N N; Wurster, C M; Todd, C D

    2010-09-15

    The chemical signals in the sequential layers of fish otoliths have the potential to provide fisheries biologists with temporal and spatial details of migration which are difficult to obtain without expensive tracking methods. Signal resolution depends, however, on the extraction technique used. We compared the use of mechanical micromilling and continuous flow isotope ratio mass spectrometry (CF-IRMS) methods with secondary ion mass spectrometry (SIMS) to obtain delta(18)O profiles from otoliths of wild Atlantic salmon (Salmo salar) and used these to corroborate the time of freshwater emigration of the juvenile with macroscopic patterns within the otolith. Both techniques showed the transition occurring at the same visible feature on the otolith, allowing future analyses to easily identify the juvenile (freshwater) versus adult (marine) life-stages. However, SIMS showed a rapid and abrupt transition whereas micromilling provided a less distinct signal. The number of samples that could be obtained per unit area sampled using SIMS was 2 to 3 times greater than that when using micromilling/CF-IRMS although the delta(18)O values and analytical precisions (approximately 0.2 per thousand) of the two methods were comparable. In addition, SIMS delta(18)O results were used to compare otolith aragonite values with predicted values calculated using various isotope fractionation equations. PMID:20740522

  13. Determination of the total and extractable mass fractions of cadmium and lead in mineral feed by using isotope dilution inductively coupled plasma mass spectrometry.

    PubMed

    Vassileva, Emilia; Hoenig, Michel

    2011-09-01

    This paper describes the determination of the total and extractable mass fractions of Cd and Pb in mineral feed test sample distributed by the Community Reference Laboratory for Heavy Metals in Feed and Food (CRL-HM), in the frame of the fifth interlaboratory comparison for the European Union National Reference Laboratories (NRL). The developed in this study protocol for the total and extractable mass fractions of Pb and Cd in mineral feed sample is based on isotope dilution inductively coupled plasma mass spectrometry (ID ICP-MS). The applied dual spiking approach reduced by 50% the number of analytical steps. The addition of hydrofluoric acid in the digestion step was found necessary to ensure a full decomposition and complete isotope equilibration. Quadrupole inductively coupled plasma mass spectrometer equipped with collision reaction interface (CRI) was employed for the measurements of Cd and Pb. Two methods for the determination of Cd were applied and compared. In the first one the high molybdenum content was reduced by introduction of matrix separation step followed by standard ICP-MS mode measurement, whereas in the second one CRI mode was used for the determination of Cd without preliminary matrix separation. The estimation of the combined uncertainty was performed according to the ISO guidelines. Uncertainty propagation was used as a tool for validation of proposed analytical procedure. Contributions from the correction for moisture content, sample homogeneity, procedural blank, instrumental background and dead time effects were evaluated in both cases. The largest uncertainty contributors for Cd and Pb is due to the within bottle homogeneity of the mineral feed sample - 50.3% and 90% respectively. The IUPAC data for isotope composition are the second major contributor to the combined uncertainty of the result for the total mass fraction of Cd in mineral feed - 43.3%. However, the ID ICP-MS results achieved from the two series of samples (partial and total extraction) were in excellent agreement within uncertainty, irrespective of the method used for extraction. The ID ICP-MS results for the total and extractable mass fractions of Cd and Pb in feed sample were compared with the results obtained with external calibration approach and routinely applied in the daily analytical practice of the Belgium National Reference Laboratory for trace elements in food and feed. PMID:21763806

  14. Synthesis of deuterium-labeled 17-hydroxyprogesterone suitable as an internal standard for isotope dilution mass spectrometry

    SciTech Connect

    Shimizu, K.; Yamaga, N.; Kohara, H.

    1988-03-01

    A synthesis is reported of 17-hydroxyprogesterone, labeled with four atoms of deuterium at ring C and suitable for use as an internal standard for isotope dilution mass spectrometry. Base-catalyzed equilibration of methyl 3 alpha-acetoxy-12-oxo-cholanate (III) with /sup 2/H/sub 2/O, followed by reduction of the 12-oxo group by the modified Wolff-Kisher method using (/sup 2/H)diethylene glycol and (/sup 2/H)hydrazine hydrate afforded (11,11,12,12,23,23(-2)H)lithocholic acid (V). The Meystre-Miescher degradation of the side chain of V yielded 3 alpha-hydroxy-5 beta-(11,11,12,12(-2)H)pregnan-20-one (X). Oxidation of the 3,20-enol-diacetate of X with perbenzoic acid followed by saponification afforded 3 alpha,17-dihydroxy-5 beta-(11,11,12,12(-2)H)pregnan-20-one (XI). Oxidation of XI with N-bromoacetamide yielded 17-hydroxy-5 beta-(11,11,12,12(-2)H)pregnane-3,20-dione (XII). Bromination of XII followed by dehydrobromination yielded 17-hydroxy-(11,11,12,12(-2)H) progesterone (XIV), consisting of 0.3% /sup 2/H0-, 1.1% /sup 2/H/sub 1/-, 8.6% /sup 2/H/sub 2/-, 37.1% /sup 2/H/sub 3/-, 52.1% /sup 2/H/sub 4/-, and 0.8% /sup 2/H/sub 5/-species.

  15. Ambient ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Lebedev, A. T.

    2015-07-01

    Ambient ionization mass spectrometry emerged as a new scientific discipline only about ten years ago. A considerable body of information has been reported since that time. Keeping the sensitivity, performance and informativity of classical mass spectrometry methods, the new approach made it possible to eliminate laborious sample preparation procedures and triggered the development of miniaturized instruments to work directly in the field. The review concerns the theoretical foundations and design of ambient ionization methods. Their advantages and drawbacks, as well as prospects for application in chemistry, biology, medicine, environmetal analysis, etc., are discussed. The bibliography includes 194 references.

  16. High-sensitivity mass spectrometry with a tandem accelerator

    SciTech Connect

    Henning, W.

    1983-01-01

    The characteristic features of accelerator mass spectrometry are discussed. A short overview is given of the current status of mass spectrometry with high-energy (MeV/nucleon) heavy-ion accelerators. Emphasis is placed on studies with tandem accelerators and on future mass spectrometry of heavier isotopes with the new generation of higher-voltage tandems.

  17. Nanopore Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Stein, Derek; Bush, Joseph; Mihovilovic, Mirna; Maulbetsch, William; Moon, Wooyoung; Bazemore-Walker, Carthene; Weber, Peter

    2012-02-01

    We describe a concept for single-DNA analysis called nanopore mass spectrometry, which seeks to combine the benefits of nanopores with the speed, sensitivity, and robustness of single base detection by mass spectrometry. The basic idea is to cleave the individual nucleotides from a DNA polymer as they transit a nanopore in sequence, and to identify each one by determining its charge-to-mass ratio in a mass spectrometer. We describe how nanopore mass spectrometry can addresse the challenges faced by other nanopore-based DNA analysis approaches. We also describe the design, construction, and testing of a prototype instrument that interfaces a nanopore ion source with a quadrupole mass filter and a single ion detector. We are using this new instrument to test the key scientific questions bearing on our analysis strategy: 1) Can DNA nucleotides be reliably transferred from their native liquid phase into the vacuum environment of a mass spectrometer? 2) Can nucleotides be detected with near 100% efficiency? 3) Can DNA polymers be controllably cleaved to isolate ionized bases or nucleotides in the mass spectrometer?

  18. Demonstration of femtosecond laser ablation inductively coupled plasma mass spectrometry for uranium isotopic measurements in U-10Mo nuclear fuel foils

    SciTech Connect

    Havrilla, George Joseph; Gonzalez, Jhanis

    2015-06-10

    The use of femtosecond laser ablation inductively coupled plasma mass spectrometry was used to demonstrate the feasibility of measuring the isotopic ratio of uranium directly in U-10Mo fuel foils. The measurements were done on both the flat surface and cross sections of bare and Zr clad U-10Mo fuel foil samples. The results for the depleted uranium content measurements were less than 10% of the accepted U235/238 ratio of 0.0020. Sampling was demonstrated for line scans and elemental mapping over large areas. In addition to the U isotopic ratio measurement, the Zr thickness could be measured as well as trace elemental composition if required. A number of interesting features were observed during the feasibility measurements which could provide the basis for further investigation using this methodology. The results demonstrate the feasibility of using fs-LA-ICP-MS for measuring the U isotopic ratio in U-10Mo fuel foils.

  19. Analytical mass spectrometry

    SciTech Connect

    Not Available

    1990-01-01

    This 43rd Annual Summer Symposium on Analytical Chemistry was held July 24--27, 1990 at Oak Ridge, TN and contained sessions on the following topics: Fundamentals of Analytical Mass Spectrometry (MS), MS in the National Laboratories, Lasers and Fourier Transform Methods, Future of MS, New Ionization and LC/MS Methods, and an extra session. (WET)

  20. Analytical mass spectrometry. Abstracts

    SciTech Connect

    Not Available

    1990-12-31

    This 43rd Annual Summer Symposium on Analytical Chemistry was held July 24--27, 1990 at Oak Ridge, TN and contained sessions on the following topics: Fundamentals of Analytical Mass Spectrometry (MS), MS in the National Laboratories, Lasers and Fourier Transform Methods, Future of MS, New Ionization and LC/MS Methods, and an extra session. (WET)

  1. A novel quantification strategy of transferrin and albumin in human serum by species-unspecific isotope dilution laser ablation inductively coupled plasma mass spectrometry (ICP-MS).

    PubMed

    Feng, Liuxing; Zhang, Dan; Wang, Jun; Shen, Dairui; Li, Hongmei

    2015-07-16

    Species-specific (SS) isotope dilution analysis with gel electrophoresis (GE)-laser ablation (LA)-ICP-MS is a promising technique for the quantification of particular metal-binding proteins in biological samples. However, unavailable isotopically enriched spike and metal losses in GE separation are main limitations for SS-isotope dilution PAGE-LA-ICP-MS. In this study, we report for the first time the absolute quantification of transferrin (Tf) and albumin (Alb) in human serum by non-denaturing (native) GE combined with species-unspecific isotope dilution mass spectrometry (IDMS). In order to achieve a homogeneous distribution of both protein and isotope-enriched spike (simulated isotope equilibration), immersing the protein strips with (34)S spike solution after gel electrophoresis was demonstrated to be an effective way of spike addition. Furthermore, effects of immersion time and (34)S spike concentration were investigated to obtain optimal conditions of the post-electrophoresis isotope dilution method. The relative mass of spike and ablated sample (m(sp)/m(sam)) in IDMS equation was calculated by standard Tf and Alb proteins, which could be applied to the quantification of Tf and Alb in ERM-DA470k/IFCC for method confirmation. The results were in agreement with the certified value with good precision and small uncertainty (1.5-3%). In this method, species-specific spike protein is not necessary and the integrity of the heteroatom-protein could be maintained in sample preparation process. Moreover, the application of species-unspecific isotope dilution GE-LA-ICP-MS has the potential to offer reliable, direct and simultaneous quantification of proteins after conventional 1D and 2D gel electrophoretic separations. PMID:26073803

  2. MASS SPECTROMETRY IN ENVIRONMENTAL SCIENCES

    EPA Science Inventory

    This review covers applications of mass spectrometry to the environmental sciences. From the early applications of mass spectrometry to environmental research in the 1960s and 1970s, mass spectrometry has played an important role in aiding our understanding of environmental poll...

  3. Determination of the 87Sr/86Sr isotope ratio in USGS silicate reference materials by multi-collector ICP-mass spectrometry

    NASA Astrophysics Data System (ADS)

    Balcaen, Lieve; Schrijver, Isabel De; Moens, Luc; Vanhaecke, Frank

    2005-04-01

    Multi-collector ICP-mass spectrometry (MC-ICP-MS) was used for 87Sr/86Sr isotope ratio determination in newly introduced silicate reference materials from the US Geological Survey (USGS): granite G-3, andesite AGV-2, and basalt BCR-2. Next to the SrCO3 isotopic standard NIST SRM 987, also analogous USGS reference materials from the previous generation, and for which reference 87Sr/86Sr data obtained by TIMS are available, were analysed for validation purposes. Sample preparation consisted of acid digestion and subsequent isolation of Sr by means of a dedicated and commercially available crown ether-based resin. The Sr fractions thus obtained were analysed via MC-ICP-MS whereby mass discrimination was corrected for internally, while the isobaric interference at a mass-to-charge ratio of 86 caused by Kr impurities in the Ar gas was mathematically corrected for by using the signal for a Kr isotope free from spectral overlap. Finally, also the effect of the small amount of Rb that may still be present in the Sr fraction was corrected for mathematically on the basis of the signal intensity for 85Rb. The MC-ICP-MS results for G-2, AGV-1 and BCR-1 showed an excellent agreement with the corresponding TIMS values (<0.003% bias in all cases), such that it can be assumed that also the 87Sr/86Sr isotope ratio results obtained for the new reference materials are reliable.

  4. Biological Cluster Mass Spectrometry

    PubMed Central

    Winograd, Nicholas; Garrison, Barbara J.

    2010-01-01

    This article reviews the new physics and new applications of secondary ion mass spectrometry using cluster ion probes. These probes, particularly C60, exhibit enhanced molecular desorption with improved sensitivity owing to the unique nature of the energy-deposition process. In addition, these projectiles are capable of eroding molecular solids while retaining the molecular specificity of mass spectrometry. When the beams are microfocused to a spot on the sample, bioimaging experiments in two and three dimensions are feasible. We describe emerging theoretical models that allow the energy-deposition process to be understood on an atomic and molecular basis. Moreover, experiments on model systems are described that allow protocols for imaging on biological materials to be implemented. Finally, we present recent applications of imaging to biological tissue and single cells to illustrate the future directions of this methodology. PMID:20055679

  5. New commercial method for the enzymatic determination of creatinine in serum and urine evaluated: Comparison with a kinetic Jaffe method and isotope dilution-mass spectrometry

    SciTech Connect

    Lindbaeck, B.B.; Bergman, A.

    1989-05-01

    We evaluated a new, simple, enzymatic kinetic method from Wako Chemicals GmbH in comparison with a kinetic Jaffe method by using isotope dilution-mass spectrometry (ID-MS) as a reference method. An ID-MS-calibrated serum standard was used. Both the enzymatic and the Jaffe method correlated well with ID-MS, except for sera with high concentrations of bilirubin. Ethyl acetoacetate, acetone, and glucose in serum interfered somewhat with the Jaffe method but not with the enzymatic method. We conclude that the present enzymatic method has merit as compared with a Jaffe method for routine work, but is more expensive.

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

    PubMed Central

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

    2014-01-01

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

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

    PubMed

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

    2008-10-01

    Past atmospheric composition can be reconstructed by the analysis of air enclosures in polar ice cores which archive ancient air in decadal to centennial resolution. Due to the different carbon isotopic signatures of different methane sources high-precision measurements of delta13CH4 in ice cores provide clues about the global methane cycle in the past. We developed a highly automated (continuous-flow) gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS) technique for ice core samples of approximately 200 g. The methane is melt-extracted using a purge-and-trap method, then separated from the main air constituents, combusted and measured as CO2 by a conventional isotope ratio mass spectrometer. One CO2 working standard, one CH4 and two air reference gases are used to identify potential sources of isotope fractionation within the entire sample preparation process and to enhance the stability, reproducibility and accuracy of the measurement. After correction for gravitational fractionation, pre-industrial air samples from Greenland ice (1831 +/- 40 years) show a delta13C(VPDB) of -49.54 +/- 0.13 per thousand and Antarctic samples (1530 +/- 25 years) show a delta13C(VPDB) of -48.00 +/- 0.12 per thousand in good agreement with published data. PMID:18819111

  8. Easy Extraction Method To Evaluate ?13C Vanillin by Liquid Chromatography-Isotopic Ratio Mass Spectrometry in Chocolate Bars and Chocolate Snack Foods.

    PubMed

    Bononi, Monica; Quaglia, Giancarlo; Tateo, Fernando

    2015-05-20

    An easy extraction method that permits the use of a liquid chromatography-isotopic ratio mass spectrometry (LC-IRMS) system to evaluate ?(13)C of vanillin in chocolate products and industrial flavorings is presented. The method applies the determination of stable isotopes of carbon to discriminate between natural vanillin from vanilla beans and vanillin from other sources (mixtures from beans, synthesis, or biotechnology). A series of 13 chocolate bars and chocolate snack foods available on the Italian market and 8 vanilla flavorings derived from industrial quality control processes were analyzed. Only 30% of products considered in this work that declared "vanilla" on the label showed data that permitted the declaration "vanilla" according to European Union (EU) Regulation 1334/2008. All samples not citing "vanilla" or "natural flavoring" on the label gave the correct declaration. The extraction method is presented with data useful for statistical evaluation. PMID:25965784

  9. Direct isotope ratio analysis of individual uranium-plutonium mixed particles with various U/Pu ratios by thermal ionization mass spectrometry.

    PubMed

    Suzuki, Daisuke; Esaka, Fumitaka; Miyamoto, Yutaka; Magara, Masaaki

    2015-02-01

    Uranium and plutonium isotope ratios in individual uranium-plutonium (U-Pu) mixed particles with various U/Pu atomic ratios were analyzed without prior chemical separation by thermal ionization mass spectrometry (TIMS). Prior to measurement, micron-sized particles with U/Pu ratios of 1, 5, 10, 18, and 70 were produced from uranium and plutonium certified reference materials. In the TIMS analysis, the peaks of americium, plutonium, and uranium ion signals were successfully separated by continuously increasing the evaporation filament current. Consequently, the uranium and plutonium isotope ratios, except the (238)Pu/(239)Pu ratio, were successfully determined for the particles at all U/Pu ratios. This indicates that TIMS direct analysis allows for the measurement of individual U-Pu mixed particles without prior chemical separation. PMID:25479434

  10. Standard test method for isotopic analysis of hydrolyzed uranium hexafluoride and uranyl nitrate solutions by thermal ionization mass spectrometry

    E-print Network

    American Society for Testing and Materials. Philadelphia

    2005-01-01

    1.1 This method applies to the determination of isotopic composition in hydrolyzed nuclear grade uranium hexafluoride. It covers isotopic abundance of 235U between 0.1 and 5.0 % mass fraction, abundance of 234U between 0.0055 and 0.05 % mass fraction, and abundance of 236U between 0.0003 and 0.5 % mass fraction. This test method may be applicable to other isotopic abundance providing that corresponding standards are available. 1.2 This test method can apply to uranyl nitrate solutions. This can be achieved either by transforming the uranyl nitrate solution to a uranyl fluoride solution prior to the deposition on the filaments or directly by depositing the uranyl nitrate solution on the filaments. In the latter case, a calibration with uranyl nitrate standards must be performed. 1.3 This test method can also apply to other nuclear grade matrices (for example, uranium oxides) by providing a chemical transformation to uranyl fluoride or uranyl nitrate solution. 1.4 This standard does not purport to address al...

  11. "Magic" Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Trimpin, Sarah

    2015-10-01

    The systematic study of the temperature and pressure dependence of matrix-assisted ionization (MAI) led us to the discovery of the seemingly impossible, initially explained by some reviewers as either sleight of hand or the misinterpretation by an overzealous young scientist of results reported many years before and having little utility. The "magic" that we were attempting to report was that with matrix assistance, molecules, at least as large as bovine serum albumin (66 kDa), are lifted into the gas phase as multiply charged ions simply by exposure of the matrix:analyte sample to the vacuum of a mass spectrometer. Applied heat, a laser, or voltages are not necessary to achieve charge states and ion abundances only previously observed with electrospray ionization (ESI). The fundamentals of how solid phase volatile or nonvolatile compounds are converted to gas-phase ions without added energy currently involves speculation providing a great opportunity to rethink mechanistic understanding of ionization processes used in mass spectrometry. Improved understanding of the mechanism(s) of these processes and their connection to ESI and matrix-assisted laser desorption/ionization may provide opportunities to further develop new ionization strategies for traditional and yet unforeseen applications of mass spectrometry. This Critical Insights article covers developments leading to the discovery of a seemingly magic ionization process that is simple to use, fast, sensitive, robust, and can be directly applied to surface characterization using portable or high performance mass spectrometers.

  12. Application of laser ablation multicollector inductively coupled plasma mass spectrometry for the measurement of calcium and lead isotope ratios in packaging for discriminatory purposes.

    PubMed

    Santamaria-Fernandez, Rebeca; Wolff, Jean-Claude

    2010-07-30

    The potential of high-precision calcium and lead isotope ratio measurements using laser ablation coupled to multicollector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) to aid distinction between four genuine and five counterfeit pharmaceutical packaging samples and further classification of counterfeit packaging samples has been evaluated. We highlight the lack of reference materials for LA-MC-ICP-MS isotope ratio measurements in solids. In this case the problem is minimised by using National Institute of Standards and Technology Standard Reference Material (NIST SRM) 915a calcium carbonate (as solid pellets) and NIST SRM610 glass disc for sample bracketing external standardisation. In addition, a new reference material, NIST SRM915b calcium carbonate, has been characterised in-house for Ca isotope ratios and is used as a reference sample. Significant differences have been found between genuine and counterfeit samples; the method allows detection of counterfeits and aids further classification of packaging samples. Typical expanded uncertainties for measured-corrected Ca isotope ratio values ((43)Ca/(44)Ca and (42)Ca/(44)Ca) were found to be below 0.06% (k = 2, 95% confidence) and below 0.2% for measured-corrected Pb isotope ratios ((207)Pb/(206)Pb and (208)Pb/(206)Pb). This is the first time that Ca isotope ratios have been measured in packaging materials using LA coupled to a multicollector (MC)-ICP-MS instrument. The use of LA-MC-ICP-MS for direct measurement of Ca and Pb isotopic variations in cardboard/ink in packaging has definitive potential to aid counterfeit detection and classification. PMID:20552700

  13. Nuclear applications of inorganic mass spectrometry.

    PubMed

    De Laeter, John

    2010-01-01

    There are several basic characteristics of mass spectrometry that are not always fully appreciated by the science community. These characteristics include the distinction between relative and absolute isotope abundances, and the influence of isotope fractionation on the accuracy of isotopic measurements. These characteristics can be illustrated in the field of nuclear physics with reference to the measurement of nuclear parameters, which involve the use of enriched isotopes, and to test models of s-, r-, and p-process nucleosynthesis. The power of isotope-dilution mass spectrometry (IDMS) to measure trace elements in primitive meteorites to produce accurate Solar System abundances has been essential to the development of nuclear astrophysics. The variety of mass spectrometric instrumentation used to measure the isotopic composition of elements has sometimes been accompanied by a lack of implementation of basic mass spectrometric protocols which are applicable to all instruments. These metrological protocols are especially important in atomic weight determinations, but must also be carefully observed in cases where the anomalies might be very small, such as in studies of the daughter products of extinct radionuclides to decipher events in the early history of the Solar System. There are occasions in which misleading conclusions have been drawn from isotopic data derived from mass spectrometers where such protocols have been ignored. It is important to choose the mass spectrometer instrument most appropriate to the proposed experiment. The importance of the integrative nature of mass spectrometric measurements has been demonstrated by experiments in which long, double beta decay and geochronological decay half-lives have been measured as an alternative to costly radioactive-counting experiments. This characteristic is also illustrated in the measurement of spontaneous fission yields, which have accumulated over long periods of time. Mass spectrometry is also a valuable tool in the determination of neutron capture cross-section measurements and the application of such determinations in Planetary Science. PMID:19877268

  14. Determination of steroid hormones in a human-serum reference material by isotope dilution--mass spectrometry: A candidate definitive method for cortisol

    SciTech Connect

    Patterson, D.G.; Patterson, M.B.; Culbreth, P.H.; Fast, D.M.; Holler, J.S.; Sampson, E.J.; Bayse, D.D.

    1984-05-01

    We report a method, based on isotope dilution--mass spectrometry, for determining cortisol in a pooled specimen of human serum. Isotopically labeled cortisol is added to 5.0 mL of serum so that the molar concentrations of labeled cortisol and unlabeled cortisol are approximately equal. The specimen and two calibration standards are extracted with dichloromethane, and the extracted cortisol is converted to the methoxime-trimethylsilyl ether derivative. Samples and standards are analyzed by gas chromatography--mass spectrometry by monitoring the peak areas for m/z 605 and 608. The cortisol concentration is calculated by linear interpolation between the two bracketing standards. Variances of data collected during six weeks showed that the overall coefficient of variation (CV) was 0.69% (n . 32); the within-vial CV, 0.63%; the among-vial CV, 0.22%; and the among-day CV, 0.15% (means . 3.973 nmol/vial). Method specificity was demonstrated by liquid chromatographic as well as C/sub 8/ mini-column cleanup of samples before derivation, by alternative ion monitoring at m/z 636 and 639, and by negative-ion chemical ionization at m/z 459 and 462. Derivatives of all observed degradation products of cortisol under basic, neutral, and acidic conditions did not interfere.

  15. Comparative analysis of S-fatty acylation of gel-separated proteins by stable isotope-coded fatty acid transmethylation and mass spectrometry.

    PubMed

    Dong, Linjie; Li, Jianjian; Li, Lun; Li, Tingting; Zhong, Hongying

    2011-09-01

    Covalent attachment of palmitic acid or other fatty acids to the thiol groups of cysteine residues of proteins through reversible thioester bonds has an important role in the regulation of diverse biological processes. We describe here the development of a mass spectrometry protocol based on stable isotope-coded fatty acid transmethylation (iFAT) for qualitative and comparative analysis of protein S-fatty acylation under different experimental conditions. In this approach, cellular proteins extracted from different cell states are separated by SDS-PAGE and then the gel is stained with either Coomassie blue or Nile red for improved sensitivity. Protein bands are excised and then an in-gel stable iFAT procedure is performed. The fatty acid methyl esters resulting from derivatization with d0- and d3-methanol are identified by mass spectrometry. By measuring the intensities of labeled and unlabeled fragment ion pairs of fatty acid methyl esters, the levels of S-fatty acylation in different cells or tissues can be compared. This approach has been applied to monitor the changes of S-fatty acylation of zebrafish liver proteome in response to environmental dichlorodiphenyltrichloroethane exposure. Compared with the approach using metabolic incorporation of radioactive fatty acid analogs, it is not only simple and effective but also eliminates the hazards of handling radioactive isotopes. PMID:21886103

  16. The use of static mass spectrometry to determine the combined stable isotopic composition of small samples of atmospheric methane.

    PubMed

    Jackson; Morgan; Morse; Butterworth; Pillinger

    1999-07-01

    Global budgets of atmospheric trace gases are increasingly being constrained by means of stable isotope measurements. Published analytical techniques for studying the parallel stable isotopic composition of methane (delta(13)C and deltaD) require prohibitively large quantities of methane for analysis, making them unsuitable for studies where sample size is small, e.g. soil methane fluxes. A highly sensitive static mass spectrometer has been developed which uniquely uses CH(4) as the analyte. The method requires only 8 ng of CH(4) for analysis (<10 mL ambient air), making replicated measurements of the isotopic composition of CH(4) in small samples feasible for the first time. This paper provides the first detailed description of the instrumentation and the analytical technique. The technique has been used to analyse small samples of air collected in Snowdonia over 21 months. The combined stable isotopic composition (delta(17)M) ranged from 29.5 to 35.5 per thousand, with an average value of 32.2 per thousand, and was strongly correlated with wind direction (p <0.01, r(2) = 0.71). Copyright 1999 John Wiley & Sons, Ltd. PMID:10407320

  17. Laser ablation molecular isotopic spectrometry of carbon isotopes

    NASA Astrophysics Data System (ADS)

    Bol?shakov, Alexander A.; Mao, Xianglei; Jain, Jinesh; McIntyre, Dustin L.; Russo, Richard E.

    2015-11-01

    Quantitative determination of carbon isotopes using Laser Ablation Molecular Isotopic Spectrometry (LAMIS) is described. Optical emission of diatomic molecules CN and C2 is used in these measurements. Two quantification approaches are presented: empirical calibration of spectra using a set of reference standards and numerical fitting of a simulated spectrum to the experimental one. Formation mechanisms of C2 and CN in laser ablation plasma are briefly reviewed to provide insights for implementation of LAMIS measurements. A simulated spectrum of the 12C2 Swan system was synthesized using four constituents within 473.5-476.5 nm. Simulation included three branches of 12C2 (1-0), branches R(0-0) and R(1-1), and branch P(9-8) of 12C2. Spectral positions of the tail lines in R(0-0) and R(1-1) were experimentally measured, since they were not accurately known before. The Swan band (1-0) of the isotopologue 13C12C was also simulated. Fitting to the experimental spectrum yielded the ratio 13C/12C = 1.08% in a good agreement with measurements by isotope ratio mass spectrometry. LAMIS promises to be useful in coal, oil and shale exploration, carbon sequestration monitoring, and agronomy studies.

  18. Correction for the 17O interference in ?(13C) measurements when analyzing CO2 with stable isotope mass spectrometry

    USGS Publications Warehouse

    Coplen, Tyler B.; Brand, Willi A.; Assonov, Sergey S.

    2010-01-01

    Measurements of ?(13C) determined on CO2 with an isotope-ratio mass spectrometer (IRMS) must be corrected for the amount of 17O in the CO2. For data consistency, this must be done using identical methods by different laboratories. This report aims at unifying data treatment for CO2 IRMS by proposing (i) a unified set of numerical values, and (ii) a unified correction algorithm, based on a simple, linear approximation formula. Because the oxygen of natural CO2 is derived mostly from the global water pool, it is recommended that a value of 0.528 be employed for the factor ?, which relates differences in 17O and 18O abundances. With the currently accepted N(13C)/N(12C) of 0.011 180(28) in VPDB (Vienna Peedee belemnite) reevaluation of data yields a value of 0.000 393(1) for the oxygen isotope ratio N(17O)/N(16O) of the evolved CO2. The ratio of these quantities, a ratio of isotope ratios, is essential for the 17O abundance correction: [N(17O)/N(16O)]/[N(13C)/N(12C)] = 0.035 16(8). The equation [?(13C) ? 45?VPDB-CO2 + 2 17R/13R (45?VPDB-CO2 – ?46?VPDB-CO2)] closely approximates ?(13C) values with less than 0.010 ‰ deviation for normal oxygen-bearing materials and no more than 0.026 ‰ in extreme cases. Other materials containing oxygen of non-mass-dependent isotope composition require a more specific data treatment. A similar linear approximation is also suggested for ?(18O). The linear approximations are easy to implement in a data spreadsheet, and also help in generating a simplified uncertainty budget.

  19. Isotopic analysis of Cu in blood serum by multi-collector ICP-mass spectrometry: a new approach for the diagnosis and prognosis of liver cirrhosis?

    PubMed

    Costas-Rodríguez, Marta; Anoshkina, Yulia; Lauwens, Sara; Van Vlierberghe, Hans; Delanghe, Joris; Vanhaecke, Frank

    2015-03-01

    The isotopic composition of blood serum Cu has been investigated as a potential parameter for the diagnosis and prognosis of liver cirrhosis. Serum samples from supposedly healthy women (reference population) and from a group of female patients suffering from liver cirrhosis of different etiologies were analysed. The procedure for isolation of serum Cu and the measurement protocol for its isotopic analysis by multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS) were evaluated. Significant differences in the isotopic composition of Cu were observed between the reference population and the patients. A wide spread in ?(65)Cu was observed within the cirrhosis population and ?(65)Cu seems to be linked to the severity of the disease. Patients with end-stage liver disease showed a significantly lighter serum Cu isotopic composition. Many clinical parameters used for the diagnosis and monitoring of liver diseases, i.e. the levels of aspartate aminotransferase, De Ritis ratio, prothrombin and international normalized ratio, albumin, bilirubin, Na and C-reactive protein, correlate well with the ?(65)Cu values, as did the ceruloplasmin level and the ceruloplasmin/Cu concentration ratio. The isotopic composition of serum Cu appears to reveal the synthetic and hepatocellular function of the liver synergistically with inflammation and fluid retention in the cohort studied. A relevant relationship was also observed between ?(65)Cu and scores of mortality risk, such as the Model for End-stage Liver Disease (MELD) and MELD-Na. Thus, the isotopic composition of serum Cu shows potential as a new approach for the prognosis of liver disease, and although further investigation is required, for evaluation of the mortality risk in end-stage liver disease and prioritization of liver transplants. PMID:25644127

  20. High-resolution twin-ion metabolite extraction (HiTIME) mass spectrometry: nontargeted detection of unknown drug metabolites by isotope labeling, liquid chromatography mass spectrometry, and automated high-performance computing.

    PubMed

    Leeming, Michael G; Isaac, Andrew P; Pope, Bernard J; Cranswick, Noel; Wright, Christine E; Ziogas, James; O'Hair, Richard A J; Donald, William A

    2015-04-21

    The metabolic fate of a compound can often determine the success of a new drug lead. Thus, significant effort is directed toward identifying the metabolites formed from a given molecule. Here, an automated and nontargeted procedure is introduced for detecting drug metabolites without authentic metabolite standards via the use of stable isotope labeling, liquid chromatography mass spectrometry (LC/MS), and high-performance computing. LC/MS of blood plasma extracts from rats that were administered a 1:1 mixture of acetaminophen (APAP) and (13)C6-APAP resulted in mass spectra that contained "twin" ions for drug metabolites that were not detected in control spectra (i.e., no APAP administered). Because of the development of a program (high-resolution twin-ion metabolite extraction; HiTIME) that can identify twin-ions in high-resolution mass spectra without centroiding (i.e., reduction of mass spectral peaks to single data points), 9 doublets corresponding to APAP metabolites were identified. This is nearly twice that obtained by use of existing programs that make use of centroiding to reduce computational cost under these conditions with a quadrupole time-of-flight mass spectrometer. By a manual search for all reported APAP metabolite ions, no additional twin-ion signals were assigned. These data indicate that all the major metabolites of APAP and multiple low-abundance metabolites (e.g., acetaminophen hydroxy- and methoxysulfate) that are rarely reported were detected. This methodology can be used to detect drug metabolites without prior knowledge of their identity. HiTIME is freely available from https://github.com/bjpop/HiTIME . PMID:25818563

  1. Single event mass spectrometry

    DOEpatents

    Conzemius, Robert J. (Ames, IA)

    1990-01-16

    A means and method for single event time of flight mass spectrometry for analysis of specimen materials. The method of the invention includes pulsing an ion source imposing at least one pulsed ion onto the specimen to produce a corresponding emission of at least one electrically charged particle. The emitted particle is then dissociated into a charged ion component and an uncharged neutral component. The ion and neutral components are then detected. The time of flight of the components are recorded and can be used to analyze the predecessor of the components, and therefore the specimen material. When more than one ion particle is emitted from the specimen per single ion impact, the single event time of flight mass spectrometer described here furnis This invention was made with Government support under Contract No. W-7405-ENG82 awarded by the Department of Energy. The Government has certain rights in the invention.

  2. New even-parity high-lying levels of Sm I and measurement of isotope shifts by two-color resonance ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Seema, A. U.; Mandal, P. K.; Rath, Asawari D.; Dev, Vas

    2014-09-01

    In this work, we investigate the even-parity high-lying levels of Sm I in the energy region 33136-33960 cm-1 by performing two-color three-photon resonance ionization spectroscopy in an atomic beam coupled to a time-of-flight mass spectrometer using two tunable pulsed dye lasers. We observe twenty-one new and confirm eight previously reported even-parity energy levels of Sm I in this spectral region. Absolute energies of these levels are determined with an accuracy of ±0.3 cm-1. Using electric dipole selection rule, total angular momentum (J-value) of the most newly observed levels is assigned uniquely. Further, employing two-color three-step resonance ionization mass spectrometry, we measure the isotope shift between 154Sm and 144Sm of sixteen high-lying levels with a moderate accuracy of ±30 mK.

  3. Amino acid precursors from a simulated lower atmosphere of Titan, Experiments of cosmic ray energy source with 13C- and 18O-stable isotope probing mass spectrometry

    E-print Network

    Taniuchi, Toshinori; Kobayashi, Kensei

    2013-01-01

    The organic haze of aerosols that shrouds the Saturnian moon Titan has previously been studied by both observations and laboratory simulation experiments. Here we report the abiotic formation of amino acid precursors in complex organic molecules during experimental simulation of the environment near Titan's surface with proton irradiation. Pyrolysis of the organic molecules formed in the simulated Titan atmosphere by proton irradiation at 600 degree-C yielded compounds that contained HCN and NH3. These experimental results are consistent with the molecular information obtained by pyrolysis gas chromatography-mass spectrometry (pyrolysis GC-MS) of samples collected by the Huygens probe to Titan. Scanning electron microscopy (SEM) and three-dimensional atomic force microscopy (AFM) images of the irradiation products reveal nanometer-scale filaments and globules in complex amorphous structures (approximately 1000 Da). Isotope probing experiments by matrix-assisted laser desorption ionization time-of-flight mass ...

  4. Automated gravimetric sample pretreatment using an industrial robot for the high-precision determination of plutonium by isotope dilution mass spectrometry.

    PubMed

    Surugaya, Naoki; Hiyama, Toshiaki; Watahiki, Masaru

    2008-06-01

    A robotized sample-preparation method for the determination of Pu, which is recovered by extraction reprocessing of spent nuclear fuel, by isotope dilution mass spectrometry (IDMS) is described. The automated system uses a six-axis industrial robot, whose motility is very fast, accurate, and flexible, installed in a glove box. The automation of the weighing and dilution steps enables operator-unattended sample pretreatment for the high-precision analysis of Pu in aqueous solutions. Using the developed system, the Pu concentration in a HNO(3) medium was successfully determined using a set of subsequent mass spectrometric measurements. The relative uncertainty in determining the Pu concentration by IDMS using this system was estimated to be less than 0.1% (k = 2), which is equal to that expected of a talented analyst. The operation time required was the same as that for a skilled operator. PMID:18544862

  5. Method for ultra-trace cesium isotope ratio measurements from environmental samples using thermal ionization mass spectrometry

    SciTech Connect

    Snow, Mathew S.; Snyder, Darin C.; Mann, Nick R.; White, Byron M.

    2015-05-01

    135Cs/137Cs isotope ratios can provide the age, origin and history of environmental Cs contamination. Relatively high precision 135Cs/137Cs isotope ratio measurements from samples containing femtogram quantities of 137Cs are needed to accurately track contamination resuspension and redistribution following environmental 137Cs releases; however, mass spectrometric analyses of environmental samples are limited by the large quantities of ionization inhibitors and isobaric interferences which are present at relatively high concentrations in the environment. We report a new approach for Cs purification from environmental samples. An initial ammonium molybdophosphate-polyacrylonitrile (AMP-PAN) column provides a robust method for extracting Cs under a wide variety of sample matrices and mass loads. Cation exchange separations using a second AMP-PAN column result in more than two orders of magnitude greater Cs/Rb separation factors than commercially available strong cation exchangers. Coupling an AMP-PAN cation exchanging step to a microcation column (AG50W resin) enables consistent 2-4% (2?) measurement errors for samples containing 3-6,000 fg 137Cs, representing the highest precision 135Cs/137Cs ratio measurements currently reported for soil samples at the femtogram level.

  6. Molecular formula analysis of fragment ions by isotope-selective collision-induced dissociation tandem mass spectrometry of pharmacologically active compounds.

    PubMed

    Bianco, Giuliana; Buchicchio, Alessandro; Lelario, Filomena; Cataldi, Tommaso R I

    2014-12-01

    The purpose of this work is to explore the mass fragment characterization of commonly used drugs through a novel approach, which involves isotope-selective tandem mass spectrometry (MS/MS). Collision-induced dissociation (CID) was performed with a low-resolution linear ion trap mass spectrometer in positive electrospray ionization. Three pharmacologically active ingredients, i.e. omeprazole, meloxicam and brinzolamide, selected as model compounds in their own formulation, were investigated as a sodiated adduct [C17 H19 N3 O3 S?+?Na](+) (omeprazole) and as protonated adducts, [C14 H13 N3 O4 S2 ?+?H](+) and [C12 H21 N3 O5 S3 ?+?H](+) , meloxicam and brinzolamide, respectively. Selecting a narrow window of ±0.5 m/z units, precursor ion fragmentation by CID-MS/MS of isotopologues A?+?0, A?+?1 and A?+?2 was found very useful to confirm the chemical formula of product ions, thus aiding the establishment of characteristic fragmentation pathways of all three examined compounds. The correctness of putative molecular formula of product ions was easily demonstrated by exploiting the isotope peak abundance ratios (i.e. IF+0 /IF+1 and IF+0 /IF+2 ) as simple constraints in low-resolution MS instrumentations. PMID:25476951

  7. 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 ?(15)N analysis of glyphosate and AMPA were 150 and 250 ng injected, respectively. A combination of ?(15)N and ?(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

  8. Determination of lead, cadmium, indium, thallium and silver in ancient ices from Antarctica by isotope dilution-thermal ionization mass spectrometry

    USGS Publications Warehouse

    Matsumoto, A.; Hinkley, T.K.

    1997-01-01

    The concentrations of five chalcophile elements (Pb, Cd, In, Tl and Ag) and the lead isotope rarios in ancient ices from the Taylor Dome near coastal Antarctica, have been determined by the isotope dilutionthermal ionization mass spectrometry (ID-TIMS), with ultra-clean laboratory techniques. The samples were selected from segments of cores, one of which included a visible ash layer. Electric conductivity measurement (ECM) or dielectric properties (DEP) gave distinctive sharp peaks for some of the samples c hosen. Exterior portions of the sample segments were trimmed away by methods described here. Samples w ere evaporated to dryness and later separated into fractions for the five elements using an HBr-HNO3 a nion exchange column method. The concentrations are in the range 2.62-36.7 pg Pb/g of ice, 0.413-2.83 pg Cd/g, 0.081-0.34 pg In/g, 0.096-2.8 pg Tl/g and 0.15-0.84 pg Ag/g. respectively. The dispersions in duplicate analyses are about ??1% for lead and cadmium, ??2% for indium. ??4% for thallium and ??6% for silver, respectively. The concentrations of lead obtained are commonly higher than those in the present-day Antarctic surface snows, but the isotope ratios are distinctively higher than those of the present-day snows and close to those of the other ancient ice collected from a different Antarctic area.

  9. Use of Isotope Ratio Mass Spectrometry (IRMS) Determination ((18)O/(16)O) to Assess the Local Origin of Fish and Asparagus in Western Switzerland.

    PubMed

    Rossier, Joël S; Maury, Valérie; de Voogd, Blaise; Pfammatter, Elmar

    2014-10-01

    Here we present the use of isotope ratio mass spectrometry (IRMS) for the detection of mislabelling of food produced in Switzerland. The system is based on the analysis of the oxygen isotope distribution in water (?(18)O). Depending on the location on the earth, lake or groundwater has a specific isotopic distribution, which can serve as a fingerprint in order to verify whether a product has grown by means of the corresponding water. This report presents specifically the IRMS technique and the results obtained in the origin detection of fish grown in selected Swiss lakes as well as asparagus grown in Valais ground. Strengths and limitations of the method are presented for both cited products; on one hand, the technique is relatively universal for any product which contains significant water but on the other hand, it necessitates a rather heavy workload to build up a database of water ?(18)O values of products of different origins. This analytical tool is part of the concept of combating fraud currently in use in Switzerland. PMID:25437160

  10. Rapid analysis of biogenic amines from rice wine with isotope-coded derivatization followed by high performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Cai, Yiping; Sun, Zhiwei; Chen, Guang; Liu, Xiaomei; You, Jinmao; Zhang, Caiqing

    2016-02-01

    A pair of isotope-coded derivatization reagents, d0-10-methyl-acridone-2-sulfonyl chloride (d0-MASC, light form) and d3-10-methyl-acridone-2-sulfonyl chloride (d3-MASC, heavy form), were used for labeling biogenic amines (BAs). On basis of the isotope-coded derivatization, a global isotope internal standard quantitative method for determining seven BAs by high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) was developed. The d0-MASC and d3-MASC can easily label BAs under mild conditions within 15 min at 50 °C. The obtained light and heavy labeled BAs were monitored by the transitions of [M+H](+) ? 208 and [M+H](+) ? 211, respectively. Relative quantification of BAs was achieved by calculation of the peak area ratios of d0-MASC/d3-MASC labeled derivatives. Excellent linear responses for relative quantification were observed in the range of 1/10-10/1. The developed method has been successfully applied to the quantification of BAs in Chinese rice wine with recoveries ranging from 94.9% to 104.5%. PMID:26304364

  11. Development of SI-traceable C-peptide certified reference material NMIJ CRM 6901-a using isotope-dilution mass spectrometry-based amino acid analyses.

    PubMed

    Kinumi, Tomoya; Goto, Mari; Eyama, Sakae; Kato, Megumi; Kasama, Takeshi; Takatsu, Akiko

    2012-07-01

    A certified reference material (CRM) is a higher-order calibration material used to enable a traceable analysis. This paper describes the development of a C-peptide CRM (NMIJ CRM 6901-a) by the National Metrology Institute of Japan using two independent methods for amino acid analysis based on isotope-dilution mass spectrometry. C-peptide is a 31-mer peptide that is utilized for the evaluation of ?-cell function in the pancreas in clinical testing. This CRM is a lyophilized synthetic peptide having the human C-peptide sequence, and contains deamidated and pyroglutamylated forms of C-peptide. By adding water (1.00 ± 0.01) g into the vial containing the CRM, the C-peptide solution in 10 mM phosphate buffer saline (pH 6.6) is reconstituted. We assigned two certified values that represent the concentrations of total C-peptide (mixture of C-peptide, deamidated C-peptide, and pyroglutamylated C-peptide) and C-peptide. The certified concentration of total C-peptide was determined by two amino acid analyses using pre-column derivatization liquid chromatography-mass spectrometry and hydrophilic chromatography-mass spectrometry following acid hydrolysis. The certified concentration of C-peptide was determined by multiplying the concentration of total C-peptide by the ratio of the relative area of C-peptide to that of the total C-peptide measured by liquid chromatography. The certified value of C-peptide (80.7 ± 5.0) mg/L represents the concentration of the specific entity of C-peptide; on the other hand, the certified value of total C-peptide, (81.7 ± 5.1) mg/L can be used for analyses that does not differentiate deamidated and pyroglutamylated C-peptide from C-peptide itself, such as amino acid analyses and immunochemical assays. PMID:22610603

  12. Isotope ratio analysis of actinides, fission products, and geolocators by high-efficiency multi-collector thermal ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Bürger, S.; Riciputi, L. R.; Bostick, D. A.; Turgeon, S.; McBay, E. H.; Lavelle, M.

    2009-09-01

    A ThermoFisher "Triton" multi-collector thermal ionization mass spectrometer (MC-TIMS) was evaluated for trace and ultra-trace level isotope ratio analysis of actinides (uranium, plutonium, and americium), fission products and geolocators (strontium, cesium, and neodymium). Total efficiencies (atoms loaded to ions detected) of up to 0.5-2% for U, Pu, and Am, and 1-30% for Sr, Cs, and Nd can be reported employing resin bead load techniques onto flat ribbon Re filaments or resin beads loaded into a millimeter-sized cavity drilled into a Re rod. This results in detection limits of <0.1 fg (104 atoms to 105 atoms) for 239-242+244Pu, 233+236U, 241-243Am, 89,90Sr, and 134,135,137Cs, and <=1 pg for natural Nd isotopes (limited by the chemical processing blank) using a secondary electron multiplier (SEM) or multiple-ion counters (MICs). Relative standard deviations (RSD) as small as 0.1% and abundance sensitivities of 1 × 106 or better using a SEM are reported here. Precisions of RSD [approximate]0.01-0.001% using a multi-collector Faraday cup array can be achieved at sub-nanogram concentrations for strontium and neodymium and are suitable to gain crucial geolocation information. The analytical protocols reported herein are of particular value for nuclear forensic and nuclear safeguard applications.

  13. Determination of Glyphosate, its Degradation Product Aminomethylphosphonic Acid, and Glufosinate, in Water by Isotope Dilution and Online Solid-Phase Extraction and Liquid Chromatography/Tandem Mass Spectrometry

    USGS Publications Warehouse

    Meyer, Michael T.; Loftin, Keith A.; Lee, Edward A.; Hinshaw, Gary H.; Dietze, Julie E.; Scribner, Elisabeth A.

    2009-01-01

    The U.S. Geological Survey method (0-2141-09) presented is approved for the determination of glyphosate, its degradation product aminomethylphosphonic acid (AMPA), and glufosinate in water. It was was validated to demonstrate the method detection levels (MDL), compare isotope dilution to standard addition, and evaluate method and compound stability. The original method USGS analytical method 0-2136-01 was developed using liquid chromatography/mass spectrometry and quantitation by standard addition. Lower method detection levels and increased specificity were achieved in the modified method, 0-2141-09, by using liquid chromatography/tandem mass spectrometry (LC/MS/MS). The use of isotope dilution for glyphosate and AMPA and pseudo isotope dilution of glufosinate in place of standard addition was evaluated. Stable-isotope labeled AMPA and glyphosate were used as the isotope dilution standards. In addition, the stability of glyphosate and AMPA was studied in raw filtered and derivatized water samples. The stable-isotope labeled glyphosate and AMPA standards were added to each water sample and the samples then derivatized with 9-fluorenylmethylchloroformate. After derivatization, samples were concentrated using automated online solid-phase extraction (SPE) followed by elution in-line with the LC mobile phase; the compounds separated and then were analyzed by LC/MS/MS using electrospray ionization in negative-ion mode with multiple-reaction monitoring. The deprotonated derivatized parent molecule and two daughter-ion transition pairs were identified and optimized for glyphosate, AMPA, glufosinate, and the glyphosate and AMPA stable-isotope labeled internal standards. Quantitative comparison between standard addition and isotope dilution was conducted using 473 samples analyzed between April 2004 and June 2006. The mean percent difference and relative standard deviation between the two quantitation methods was 7.6 plus or minus 6.30 (n = 179), AMPA 9.6 plus or minus 8.35 (n = 206), and glufosinate 9.3 plus or minus 9.16 (n = 16). The analytical variation of the method, comparison of quantitation by isotope dilution and multipoint linear regressed standard curves, and method detection levels were evaluated by analyzing six sets of distilled-water, groundwater, and surface-water samples spiked in duplicate at 0.0, 0.05, 0.10 and 0.50 microgram per liter and analyzed on 6 different days during 1 month. The grand means of the normalized concentration percentage recovery for glyphosate, AMPA, and glufosinate among all three matrices and spiked concentrations ranged from 99 to 114 plus or minus 2 to 7 percent of the expected spiked concentration. The grand mean of the percentage difference between concentrations calculated by standard addition and linear regressed multipoint standard curves ranged from 8 to 15 plus or minus 2 to 9 percent for the three compounds. The method reporting levels calculated from all the 0.05- microgram per liter spiked samples were 0.02 microgram per liter for all three compounds. Compound stability experiments were conducted on 10 samples derivatized four times for periods between 136 to 269 days. The glyphosate and AMPA concentrations remained relatively constant in samples held up to 136 days before derivatization. The half life of glyphosate varied from 169 to 223 days in the underivatized samples. Derivatized samples were analyzed the day after derivitization, and again 54 and 64 days after derivatization. The derivatized samples analyzed at days 52 and 64 were within 20 percent of the concentrations of the derivatized samples analyzed the day after derivatization.

  14. Mass spectrometry in ionospheric research.

    PubMed

    Ferguson, Eldon E

    2007-01-01

    Mass spectrometry played a key role in the development of the understanding of the earth's ionosphere. Of primary importance was its use for in situ atmospheric measurements of the ion and neutral composition of the atmosphere. Mass spectrometry has also played an essential role in the laboratory measurement of critical ionospheric molecular processes. Examples of both are given. PMID:17099890

  15. Strontium isotope ratios (87Sr/86Sr) of tooth enamel: a comparison of solution and laser ablation multicollector inductively coupled plasma mass spectrometry methods.

    PubMed

    Copeland, Sandi R; Sponheimer, Matt; le Roux, Petrus J; Grimes, Vaughan; Lee-Thorp, Julia A; de Ruiter, Darryl J; Richards, Michael P

    2008-10-01

    Strontium isotope ratios (87Sr/86Sr) in tooth enamel provide a means to investigate migration and landscape use in humans and other animals. Established methods for measuring (87)Sr/(86)Sr in teeth use bulk sampling (5-20 mg) and labor-intensive elemental purification procedures before analysis by either thermal ionization mass spectrometry (TIMS) or multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS). Another method for measuring 87Sr/86Sr is laser ablation MC-ICP-MS, but concerns have been expressed about its accuracy for measuring tooth enamel. In this study we test the precision and accuracy of the technique by analyzing 30 modern rodent teeth from the Sterkfontein Valley, South Africa by laser ablation MC-ICP-MS and solution MC-ICP-MS. The results show a mean difference in 87Sr/86Sr measured by laser ablation and by solution of 0.0003 +/- 0.0002. This degree of precision is well within the margin necessary for investigating the potential geographic origins of humans or animals in many areas of the world. Because laser ablation is faster, less expensive, and less destructive than bulk sampling solution methods, it opens the possibility for conducting 87Sr/86Sr analyses of intra-tooth samples and small and/or rare specimens such as micromammal and fossil teeth. PMID:18803330

  16. Direct determination of fatty acid esters of 3-chloro-1, 2-propanediol in edible vegetable oils by isotope dilution - ultra high performance liquid chromatography - triple quadrupole mass spectrometry.

    PubMed

    Li, Heli; Chen, Dawei; Miao, Hong; Zhao, Yunfeng; Shen, Jianzhong; Wu, Yongning

    2015-09-01

    A selective and sensitive ultra-high performance liquid chromatography - triple quadrupole mass spectrometry (UHPLC-MS/MS) method coupled with matrix solid phase dispersion (MSPD) extraction was developed for the direct determination of fatty acid esters of 3-chloro-1,2-propanediol (3-MCPD esters) in edible vegetable oils. The method integrated the isotope dilution technique, MSPD extraction and UHPLC - MS/MS analysis with multi-reaction monitoring mode (MRM). Matrix-matched calibration curves showed good linearity within the range of 0.01-10mgL(-1) with the correlation coefficient not less than 0.999. Limits of detection (LODs) and limit of quantification (LOQs) of the 3-MCPD esters fell into the range of 0.0001-0.02mgkg(-1) and 0.0004-0.05mgkg(-1), respectively. The recoveries for the spiked extra virgin olive oils ranged from 94.4% to 108.3%, with the relative standard deviations (RSD) ranging from 0.6% to 10.5%. The method was applied for the oil sample (T2642) of the official Food Analysis Performance Assessment Scheme (FAPAS) in 2014 and other real samples from supermarket, and the results showed that the present method was comparative to the gas chromatography-mass spectrometry (GC-MS) method based on the improved German Society for Fat Science (DGF) standard method C-III 18 (09) except for palm oil. PMID:26239698

  17. Airborne measurements of sulfur dioxide, dimethyl sulfide, carbon disulfide, and carbonyl sulfide by isotope dilution gas chromatography/mass spectrometry

    NASA Technical Reports Server (NTRS)

    Bandy, Alan R.; Thornton, Donald C.; Driedger, Arthur R., III

    1993-01-01

    A gas chromatograph/mass spectrometer is described for determining atmospheric sulfur dioxide, carbon disulfide, dimethyl sulfide, and carbonyl sulfide from aircraft and ship platforms. Isotopically labelled variants of each analyte were used as internal standards to achieve high precision. The lower limit of detection for each species for an integration time of 3 min was 1 pptv for sulfur dioxide and dimethyl sulfide and 0.2 pptv for carbon disulfide and carbonyl sulfide. All four species were simultaneously determined with a sample frequency of one sample per 6 min or greater. When only one or two species were determined, a frequency of one sample per 4 min was achieved. Because a calibration is included in each sample, no separate calibration sequence was needed. Instrument warmup was only a few minutes. The instrument was very robust in field deployments, requiring little maintenance.

  18. The assay of pterostilbene in spiked matrices by liquid chromatography tandem mass spectrometry and isotope dilution method.

    PubMed

    Mazzotti, Fabio; Di Donna, Leonardo; Benabdelkamel, Hicham; Gabriele, Bartolo; Napoli, Anna; Sindona, Giovanni

    2010-04-01

    Pterostilbene (trans-3,5-dimethoxy-4-hydroxystilbene) is an active component found in several plant species, exhibiting important pharmacological properties. A new and reliable method of assaying this phyto compound in various matrices is presented; the assay is based on (1) the selectivity of liquid chromatography (LC) hyphenated with electrospray ionisation (ESI), (2) the specificity of a two-step mass spectrometric analysis (MS/MS) and (3) the accuracy of the isotope dilution method. The labelled analogue may be conveniently synthesised in a few steps. The sensitivity of the method is confirmed by the very low limit of detection (LOD) and limit of quantitation (LOQ) values achieved in the assay of pterostilbene in two distinct fortified matrices, and is further supported by the observed accuracy values. PMID:20198601

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

    NASA Astrophysics Data System (ADS)

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

    2009-11-01

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

  20. Oxygen isotopic distribution along the otolith growth axis by secondary ion mass spectrometry: Applications for studying ontogenetic change in the depth inhabited by deep-sea fishes

    NASA Astrophysics Data System (ADS)

    Shiao, Jen-Chieh; Itoh, Shoichi; Yurimoto, Hisayoshi; Iizuka, Yoshiyuki; Liao, Yun-Chih

    2014-02-01

    This study using tuna otoliths as working standards established a high lateral resolution and precision analysis to measure ?18Ootolith by secondary ion mass spectrometry. This analytical approach of the ion probe was applied to deep-sea fishes to reconstruct the likely depths inhabited by the fishes at different life history stages based on the measured ?18Ootolith values as a proxy of water temperature. Dramatic increases up to 5-6‰ in ?18Ootolith, representing a temperature decrease of approximately 20 °C, were detected in a blind cusk eel (Barathronus maculatus) otolith and in the otoliths of Synaphobranchus kaupii during leptocephalus metamorphosis to glass eel, inferred from the drop of otolith Sr/Ca ratios and increase of otolith growth increment width. ?18Ootolith profiles clearly divided the fish's life history into a planktonic stage in the mixed layer of the ocean and a benthic stage on the deep-sea ocean bottom. The habitat shift signal was recorded within a 150 ?m width of otolith growth zone, which was too narrow to be clearly detected by mechanical drilling and conventional isotopic ratio mass spectrometry. However, variations down to -7‰ were found in ?18Ootolith profiles as the result of Cs2+ beam sputter in the core and larval portions of the otoliths. Carbon mapping by electron probe microanalyzer and staining by toluidine blue suggested abundant proteins existed in the areas with anomaly negative ?18Ootolith values, which cannot be interpreted as a habitat change but due to the isotopic fractionation by O emission from the proteins. These results implied that careful design and understanding of the chemical composition of the analytical areas or tracks on the heterogeneous otolith was essential for highly accurate and precise analysis.

  1. Analysis of cytochrome P450 metabolites of arachidonic acid by stable isotope probe labeling coupled with ultra high-performance liquid chromatography/mass spectrometry.

    PubMed

    Zhu, Quan-Fei; Hao, Yan-Hong; Liu, Ming-Zhou; Yue, Jiang; Ni, Jian; Yuan, Bi-Feng; Feng, Yu-Qi

    2015-09-01

    Cytochrome P450 metabolites of arachidonic acid (AA) belong to eicosanoids and are potent lipid mediators of inflammation. It is well-known that eicosanoids play an important role in numerous pathophysiological processes. Therefore, quantitative analysis of cytochrome P450 metabolites of AA, including hydroxyeicosatetraenoic acids (HETEs), epoxyeicosatreinoic acids (EETs), and dihydroxyeicosatrienoic acids (DHETs) can provide crucial information to uncover underlying mechanisms of cytochrome P450 metabolites of AA related diseases. Herein, we developed a highly sensitive method to identify and quantify HETEs, EETs, and DHETs in lipid extracts of biological samples based on stable isotope probe labeling coupled with ultra high-performance liquid chromatography/mass spectrometry. To this end, a pair of stable isotope probes, 2-dimethylaminoethylamine (DMED) and d4-2-dimethylaminoethylamine (d4-DMED), were utilized to facilely label eicosanoids. The heavy labeled eicosanoid standards were prepared and used as internal standards for quantification to minimize the matrix and ion suppression effects in mass spectrometry analysis. In addition, the detection sensitivities of DMED labeled eicosanoids improved by 3-104 folds in standard solution and 5-138 folds in serum matrix compared with unlabeled analytes. Moreover, a good separation of eicosanoids isomers was achieved upon DMED labeling. The established method provided substantial sensitivity (limit of quantification at sub-picogram), high specificity, and broad linear dynamics range (3 orders of magnitude). We further quantified cytochrome P450 metabolites of AA in rat liver, heart, brain tissues and human serum using the developed method. The results showed that 19 eicosanoids could be distinctly detected and the contents of 11-, 15-, 16-, 20-HETE, 5,6-EET, and 14,15-EET in type 2 diabetes mellitus patients and 5-, 11-, 12-, 15-, 16-, 20-HETE, 8,9-EET, and 5,6-DHET in myeloid leukemia patients had significant changes, demonstrating that these eicosanoids may have important roles on the pathogenesis of type 2 diabetes mellitus and myeloid leukemia. PMID:26253834

  2. Accelerator Mass Spectrometry of Actinides in Ground- and Seawater: An Innovative Method Allowing for the Simultaneous Analysis of U, Np, Pu, Am, and Cm Isotopes below ppq Levels.

    PubMed

    Quinto, Francesca; Golser, Robin; Lagos, Markus; Plaschke, Markus; Schäfer, Thorsten; Steier, Peter; Geckeis, Horst

    2015-06-01

    (236)U, (237)Np, and Pu isotopes and (243)Am were determined in ground- and seawater samples at levels below ppq (fg/g) with a maximum sample size of 250 g. Such high sensitivity was possible by using accelerator mass spectrometry (AMS) at the Vienna Environmental Research Accelerator (VERA) with extreme selectivity and recently improved efficiency and a significantly simplified separation chemistry. The use of nonisotopic tracers was investigated in order to allow for the determination of (237)Np and (243)Am, for which isotopic tracers either are rarely available or suffer from various isobaric mass interferences. In the present study, actinides were concentrated from the sample matrix via iron hydroxide coprecipitation and measured sequentially without previous chemical separation from each other. The analytical method was validated by the analysis of the Reference Material IAEA 443 and was applied to groundwater samples from the Colloid Formation and Migration (CFM) project at the deep underground rock laboratory of the Grimsel Test Site (GTS) and to natural water samples affected solely by global fallout. While the precision of the presented analytical method is somewhat limited by the use of nonisotopic spikes, the sensitivity allows for the determination of ?10(5) atoms in a sample. This provides, e.g., the capability to study the long-term release and retention of actinide tracers in field experiments as well as the transport of actinides in a variety of environmental systems by tracing contamination from global fallout. PMID:25938849

  3. A Method Revealing Bacterial Cell-wall Architecture by Time-dependent Isotope Labeling and Quantitative Liquid Chromatography/Mass Spectrometry

    PubMed Central

    Patti, Gary J.; Chen, Jiawei; Gross, Michael L.

    2009-01-01

    The molecular details of the biosynthesis and resulting architecture of the bacterial cell wall remain unclear but are essential to understanding the activity of glycopeptide antibiotics, the recognition of pathogens by hosts, and the processes of bacterial growth and division. Here we report a new strategy to elucidate bacterial cell-wall architecture based on time-dependent isotope labeling of bacterial cells quantified by liquid chromatography/accurate mass measurement mass spectrometry. The results allow us to track the fate of cell-wall precursors (which contain the vancomycin-binding site) in Enterococcus faecium, a leading antibiotic-resistant pathogen. By comparing isotopic enrichments of post-insertionally modified cell-wall precursors, we find that tripeptides and species without Asx bridges are specific to mature cell wall. Additionally, we find that the sequence of cell-wall maturation varies throughout a cell cycle. We suggest that actively dividing E. faecium cells have three zones of unique peptidoglycan processing. Our results reveal new organizational characteristics of the bacterial cell wall that are important to understanding tertiary structure and designing novel drugs for antibiotic-resistant pathogens. PMID:19281243

  4. An analytical system for studying the stable isotopes of carbon monoxide using continuous flow-isotope ratio mass spectrometry (CF-IRMS)

    NASA Astrophysics Data System (ADS)

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

    2015-02-01

    In the atmosphere, carbon monoxide (CO) is the major sink for the hydroxyl radical (OH •), has multiple anthropogenic and natural sources and considerable spatial and seasonal variability. Measurements of CO isotopic composition are useful in constraining the strengths of its individual source and sink processes and thus its global cycle. A fully automated system for ?13C and ?18O analysis has been developed to extract CO from an air sample, convert CO into carbon dioxide (CO2) using the Schütze reagent, and then determine the isotopic composition in an isotope ratio mass spectrometer (IRMS). The entire system is continuously flushed with high-purity helium (He), the carrier gas. The blank signal of the Schütze reagent is only 1-3% of the typical sample size. The repeatability is 0.1‰ for ?13C and 0.2‰ for ?18O. The peak area allows simultaneous determination of the mole fraction with an analytical repeatability of ~0.7 nmol mol-1 for 100 mL of typical ambient air (185.4 nmol mol-1 of CO). A single, automated, measurement is performed in 18 min, so multiple measurements can be combined conveniently to improve precision.

  5. Ultratrace Uranium Fingerprinting with Isotope Selective Laser Ionization Spectrometry

    SciTech Connect

    Ziegler, Summer L.; Bushaw, Bruce A.

    2008-08-01

    Uranium isotope ratios can provide source information for tracking uranium contamination in a variety of fields, ranging from occupational bioassay to monitoring aftereffects of nuclear accidents. We describe the development of Isotope Selective Laser Ionization Spectrometry (ISLIS) for ultratrace measurement of the minor isotopes 234U, 235U, and 236U with respect to 238U. Optical isotopic selectivity in three-step excitation with single-mode continuous wave lasers is capable of measuring the minor isotopes at relative abundances below 1 ppm, and is not limited by isobaric interferences such as 235UH+ during measurement of 236U. This relative abundance limit approaches the threshold for measurement of uranium minor isotopes with conventional mass spectrometry, typically 10-7, but without mass spectrometric analysis of the laser-created ions. Uranyl nitrate standards from an international blind comparison were used to test analytical performance for different isotopic compositions and with quantities ranging from 11 ng to 10 µg total uranium. Isotopic ratio determination was demonstrated over a linear dynamic range of 7 orders of magnitude with a few percent relative precision and detection limits below 500 fg for the minor isotopes.

  6. Measurement of ?18O, ?17O, and 17O-excess in Water by Off-Axis Integrated Cavity Output Spectroscopy and Isotope Ratio Mass Spectrometry

    PubMed Central

    Berman, Elena S.F.; Levin, Naomi E.; Landais, Amaelle; Li, Shuning; Owano, Thomas

    2013-01-01

    Stable isotopes of water have long been used to improve understanding of the hydrological cycle, catchment hydrology, and polar climate. Recently, there has been increasing interest in measurement and use of the less-abundant 17O isotope in addition to 2H and 18O. Off-axis integrated cavity output spectroscopy (OA-ICOS) is demonstrated for accurate and precise measurements ?18O, ?17O, and 17O-excess in liquid water. OA-ICOS involves no sample conversion and has a small footprint, allowing measurements to be made by researchers collecting the samples. Repeated (514) high-throughput measurements of the international isotopic reference water standard GISP demonstrate the precision and accuracy of OA-ICOS: ?18OVSMOW-SLAP =?24.74 ± 0.07 ‰ (1?) and ?17OVSMOW-SLAP = ?13.12 ± 0.05 ‰ (1?). For comparison, the IAEA value for ?18OVSMOW-SLAP is ?24.76 ± 0.09 ‰ (1?) and an average of previously reported values for ?17OVSMOW-SLAP is ?13.12 ± 0.06 ‰ (1?). Multiple (26) high-precision measurements of GISP provide a 17O-excessVSMOW-SLAP of 23 ± 10 per meg (1?); an average of previously reported values for 17O-excessVSMOW-SLAP is 22 ± 11 per meg (1?). For all these OA-ICOS measurements, precision can be further enhanced by additional averaging. OA-ICOS measurements were compared with two independent isotope ratio mass spectrometry (IRMS) laboratories and shown to have comparable accuracy and precision as the current fluorination-IRMS techniques in ?18O, ?17O, and 17O-excess. The ability to measure accurately ?18O, ?17O, and 17O-excess in liquid water inexpensively and without sample conversion is expected to increase vastly the application of ?17O and 17O-excess measurements for scientific understanding of the water cycle, atmospheric convection, and climate modeling among others. PMID:24032448

  7. Separating Autotrophic and Heterotrophic Contributions to Soil Respiration in Maize-Based Agroecosystems Using Stable Carbon Isotope Ratio Mass Spectrometry.

    NASA Astrophysics Data System (ADS)

    Amos, B.; Walters, D. T.; Madhavan, S.; Arkebauer, T. J.; Scoby, D. L.

    2005-12-01

    Any effort to establish a carbon budget for a growing crop by means of a thorough accounting of all C sources and sinks will require the ability to discriminate between autotrophic and heterotrophic contributions to soil surface CO2 flux. Autotrophic soil respiration (Ra) is defined as combined root respiration and the respiration of soil microorganisms residing in the rhizosphere and using root-derived carbohydrates as an energy source, while heterotrophic respiration (Rh) is defined as the respiration of soil microorganisms and macroorganisms not directly under the influence of the live root system and using SOM as an energy source. We partition soil surface CO2 flux into its autotrophic and heterotrophic components by combining root exclusion with stable carbon isotope techniques in production scale (~65 ha) maize-based agroecosystems. After flux measurements, small chambers are placed on collars in both root excluded shields and in non-root excluded soil, ambient headspace CO2 is removed using a soda lime trap, and soil-respired C is allowed to collect in the chambers. Soil respiration samples are then collected in 12mL evacuated exetainers and analyzed for ?13C by means of a Finnigan Delta-S isotope ratio mass spectrometer interfaced with a Thermo Finnigan GasBench II and a cryogenic trap to increase CO2 concentration. These ?13C measurements were made throughout the 2005 growing season in maize fields representing three agroecosystems: irrigated continuous maize, irrigated maize-soybean rotation, and rainfed maize soybean rotation. Estimates of autotrophic and heterotrophic soil respiration along with other results of this study will be presented.

  8. Establishing Ion Ratio Thresholds Based on Absolute Peak Area for Absolute Protein Quantification using Protein Cleavage Isotope Dilution Mass Spectrometry

    PubMed Central

    Loziuk, Philip L.; Sederoff, Ronald R.; Chiang, Vincent L.; Muddiman, David C.

    2014-01-01

    Quantitative mass spectrometry has become central to the field of proteomics and metabolomics. Selected reaction monitoring is a widely used method for the absolute quantification of proteins and metabolites. This method renders high specificity using several product ions measured simultaneously. With growing interest in quantification of molecular species in complex biological samples, confident identification and quantitation has been of particular concern. A method to confirm purity or contamination of product ion spectra has become necessary for achieving accurate and precise quantification. Ion abundance ratio assessments were introduced to alleviate some of these issues. Ion abundance ratios are based on the consistent relative abundance (RA) of specific product ions with respect to the total abundance of all product ions. To date, no standardized method of implementing ion abundance ratios has been established. Thresholds by which product ion contamination is confirmed vary widely and are often arbitrary. This study sought to establish criteria by which the relative abundance of product ions can be evaluated in an absolute quantification experiment. These findings suggest that evaluation of the absolute ion abundance for any given transition is necessary in order to effectively implement RA thresholds. Overall, the variation of the RA value was observed to be relatively constant beyond an absolute threshold ion abundance. Finally, these RA values were observed to fluctuate significantly over a 3 year period, suggesting that these values should be assessed as close as possible to the time at which data is collected for quantification. PMID:25154770

  9. Validated measurements of the uranium isotopic signature in human urine samples using magnetic sector-field inductively coupled plasma mass spectrometry.

    PubMed

    Tresl, Ivan; De Wannemacker, Günther; Quétel, Christophe R; Petrov, Ivan; Vanhaecke, Frank; Moens, Luc; Taylor, Philip D P

    2004-01-15

    Increased interest in measuring uranium isotope ratios in environmental samples (biological materials, soils, dust particles, water) has come from the necessity to assess the health impact of the use of depleted uranium (DU) based ammunitions during recent military conflicts (e.g., Gulf war, Kosovo) and from the need to identify nondeclared nuclear activities (nuclear safeguards). In this context, very important decisions can arise which have to be based on measurement data of nondisputable uncertainty. The present study describes the certification to 2.5% (k = 2) relative combined uncertainty of n(235U)/n(238U) at ultralow uranium levels (approximately 5-20 pg g(-1)) in human urine samples. After sample decomposition and matrix separation, the isotope ratios were measured by means of a single-detector magnetic sector-field inductively coupled plasma mass spectrometry instrument fitted with an ultrasonic nebulizer. Correction for mass discrimination effects was obtained by means of the certified isotopic reference material IRMM-184. The analytical procedure developed was validated in three complementary ways. First, all major sources of uncertainty were identified and propagated together following the ISO/GUM guidelines. Second, this quality was controlled with a matrix matching NUSIMEP-3 sample (approximately 0.06-0.7% difference from certified). Third, the instrumental part of the procedure was proven to be reproducible from the confirmation of the results obtained for three samples remeasured 7 months later (approximately 1.5% difference). The results obtained for 33 individuals indicated that none seemed to have been exposed to contamination by DU. PMID:14750735

  10. Quantification of (15)N-nitrate in urine with gas chromatography combustion isotope ratio mass spectrometry to estimate endogenous NO production.

    PubMed

    Houben, Els; Hamer, Henrike M; Luypaerts, Anja; De Preter, Vicky; Evenepoel, Pieter; Rutgeerts, Paul; Verbeke, Kristin

    2010-01-15

    The use of stable isotope labeled substrates and subsequent analysis of urinary nitrate, forms a noninvasive test for evaluation of the in vivo NO metabolism. The present paper describes a new method for simultaneous quantification of (15)N-nitrate and total nitrate with gas chromatography combustion isotope ratio mass spectrometry (GC-C-IRMS). Nitrate, isolated from urine with a nitrate selective resin, was reduced to nitrite using copperized cadmium. Subsequently, Sudan I was formed by diazotation. Sudan II was added as internal standard, and both molecules were analyzed with GC-C-IRMS as tert-butyldimethylsilyl derivatives. The accuracy was determined during a recovery study of two different known nitrate concentrations and two (15)N-enrichments. A recovery of 101.6% and 103.9% for total nitrate and 107.6% and 91.2% for (15)N-nitrate was obtained, respectively. The validated method was applied on complete 72 h urine collections after intravenous administration of (15)N-nitrate and (15)N-arginine in humans. On average, 51.8% (47.0-71.0%) of administered (15)N-nitrate was excreted, while 0.68% (0.44-1.17%) of (15)N-arginine was metabolized to nitrate. In conclusion, this method can be used for accurate simultaneous determination of (15)N-nitrate and total nitrate concentrations in urine and can be applied in clinical studies for noninvasive evaluation of NO metabolism in vivo. PMID:20000695

  11. Characterization of TATP gas phase product ion chemistry via isotope labeling experiments using ion mobility spectrometry interfaced with a triple quadrupole mass spectrometer.

    PubMed

    Tomlinson-Phillips, Jill; Wooten, Alfred; Kozole, Joseph; Deline, James; Beresford, Pamela; Stairs, Jason

    2014-09-01

    Identification of the fragment ion species associated with the ion reaction mechanism of triacetone triperoxide (TATP), a homemade peroxide-based explosive, is presented. Ion mobility spectrometry (IMS) has proven to be a key analytical technique in the detection of trace explosive material. Unfortunately, IMS alone does not provide chemical identification of the ions detected; therefore, it is unknown what ion species are actually formed and separated by the IMS. In IMS, ions are primarily characterized by their drift time, which is dependent on the ion?s mass and molecular cross-section; thus, IMS as a standalone technique does not provide structural signatures, which is in sharp contrast to the chemical and molecular information that is generally obtained from other customary analytical techniques, such as NMR, Raman and IR spectroscopy and mass spectrometry. To help study the ion chemistry that gives rise to the peaks observed in IMS, the hardware of two different commercial IMS instruments has been directly coupled to triple quadrupole (QQQ) mass spectrometers, in order to ascertain each ion?s corresponding mass/charge (m/z) ratios with different dopants at two temperatures. Isotope labeling was then used to help identify and confirm the molecular identity of the explosive fragment and adduct ions of TATP. The m/z values and isotope labeling experiments were used to help propose probable molecular formulas for the ion fragments. In this report, the fragment and adduct ions m/z 58 and 240 of TATP have been confirmed to be [C3H6NH·H](+) and [TATP·NH4](+), respectively; while the fragment ions m/z 73 and 89 of TATP are identified as having the molecular formulas [C4H9NH2](+) and [C4H9O2](+), respectively. It is anticipated that the work in this area will not only help to facilitate improvements in mobility-based detection (IMS and MS), but also aid in the development and optimization of MS-based detection algorithms for TATP. PMID:24913870

  12. Background effects on Faraday collectors in gas-source mass spectrometry and implications for clumped isotope measurements

    E-print Network

    Gilli, Adrian

    , and determining mechanisms of isotopic fractionation in chemical reactions or palaeoclima- tological rare isotope.[1] It is receiving increasing interest because of its potential to solve many fundamental. This excess (expressed as the 47 value, see below for a detailed definition) is temperature-dependent and can

  13. A modified procedure for gas-source isotope ratio mass spectrometry: the long-integration dual-inlet (LIDI) methodology

    E-print Network

    Gilli, Adrian

    isotopically very different CO2 samples were analyzed. The LIDI measurements of large samples (50 to 100 mol of CO2) measured at quasi-constant beam sizes, and of small samples (1.5 to 2 mol of CO2) measured and clumped isotope measurements of CO2, the LIDI protocol allows the measurement of a much larger portion

  14. Analysis of LDEF experiment AO187-2: Chemically and isotopic measurements of micrometeoroids by secondary ion mass spectrometry

    NASA Technical Reports Server (NTRS)

    1992-01-01

    Numerous 'extended impacts' found in both leading and trailing edge capture cells have been successfully analyzed for the chemical composition of projectile residues by secondary ion mass spectrometry (SIMS). Most data have been obtained from the trailing edge cells where 45 of 58 impacts have been classified as 'probably natural' and the remainder as 'possibly man-made debris.' This is in striking contrast to leading edge cells where 9 of 11 impacts so far measured are definitely classified as orbital debris. Although all the leading edge cells had lost their plastic entrance foils during flight, the rate of foil failure was similar to that of the trailing edge cells, 10 percent of which were recovered intact. Ultra-violet embrittlement is suspected as the major cause of failure on both leading and trailing edges. The major impediment to the accurate determination of projectile chemistry is the fractionation of volatile and refractory elements in the hypervelocity impact and redeposition processes. This effect had been noticed in simulation experiment but is more pronounced in the Long Duration Exposure Facility (LDEF) capture cells, probably due to the higher average velocities of the space impacts. Surface contamination of the pure Ge surfaces with a substance rich in Si but also containing Mg and Al provides an additional problem for the accurate determination of impactor chemistry. The effect is variable, being much larger on surfaces that were exposed to space than in those cells that remained intact. Future work will concentrate on the analyses of more leading edge impacts and the development of new SIMS techniques for the measurement of elemental abundances in extended impacts.

  15. Secondary ion mass spectrometry combined with alpha track detection for isotope abundance ratio analysis of individual uranium-bearing particles.

    PubMed

    Esaka, Fumitaka; Magara, Masaaki

    2014-03-01

    Secondary ion mass spectrometry (SIMS) was used in combination with alpha track detection for the efficient analysis of uranium-bearing particles with higher (235)U abundances in environmental samples. A polycarbonate film containing particles was prepared and placed in contact with a CR-39 plastic detector. After exposure for 28 days, the detector was etched in a NaOH solution and each uranium-bearing particle was identified through observation of the alpha tracks recorded in the detector. A portion of the film containing each uranium-bearing particle was cut out and put onto a glassy carbon planchet. The films on the planchet were decomposed through plasma ashing for subsequent uranium abundance ratio analysis with SIMS. The alpha track-SIMS analysis of 10 uranium-bearing particles in a sample taken from a nuclear facility enabled n((235)U)/n((238)U) abundance ratios in the range 0.0072-0.25 to be detected, which were significantly higher than those obtained by SIMS without alpha track detection. The duration of the whole analytical process for analysis of 10 particles was about 32 days. The detection efficiency was calculated to be 27.1±6.5%, based on the analysis of the particles in uranium reference materials. The detection limits, defined as the diameter of the particle which produces alpha tracks more than one for a 28-days exposure, were estimated to be 0.8, 0.9, 1.1, 2.1 and 3.0 ?m for the particles having the same uranium abundance ratios with NBL CRM U850, U500, U350, U050 and U010 reference materials, respectively. The use of alpha track detection for subsequent SIMS analysis is an inexpensive and an efficient way to measure uranium-bearing particles with higher (235)U abundances. PMID:24468381

  16. Mass spectrometry of nanodiamonds.

    PubMed

    Houska, Jan; Panyala, Nagender Reddy; Peña-Méndez, Eladia Maria; Havel, Josef

    2009-04-01

    Detonation nanodiamonds (NDs) were studied by time-of-flight mass spectrometry (TOF MS). The formation of singly charged carbon clusters, C(n) (+), with groups of clusters at n = 1-35, n approximately 160-400 and clusters with n approximately 8000 was observed. On applying either high laser energy or ultrasound, the position and intensity of the maxima change and a new group of clusters at n approximately 70-80 is formed. High carbon clusters consist of an even number of carbons while the percentage of odd-numbered clusters is quite low (< or =5-10%). On increasing the laser energy, the maximum of ionization (at n approximately 200 carbons) is shifted towards the lower m/z values. It is suggested that this is mainly due to the disaggregation of the original NDs. However, the partial destruction of NDs is also possible. The carbon clusters (n approximately 2-35) are partially hydrogenated and the average value of the hydrogenation was 10-30%. Trace impurities in NDs like Li, B, Fe, and others were detected at high laser energy. Several matrices for ionizing NDs were examined and NDs themselves can also be used as a matrix for the ionization of various organic compounds. When NDs were used as a matrix for gold nanoparticles, the formation of various gold carbides Au(m)C(n) was detected and their stoichiometry was determined. It was demonstrated that TOF MS can be used advantageously to analyze NDs, characterize their size distribution, aggregation, presence of trace impurities and surface chemistry. PMID:19280609

  17. Quantitative determination of 8-hydroxy-2'-deoxyguanosine in human urine by isotope dilution mass spectrometry: normal levels in hemochromatosis.

    PubMed

    Holmberg, I; Stål, P; Hamberg, M

    1999-01-01

    A previously developed method for quantitative determination of 8-hydroxyguanine by gas chromatography-mass spectrometry was modified to allow measurement of 8-hydroxy-2'-deoxyguanosine in human urine. [4,5,6,8-(13)C4]8-Hydroxy-2'-deoxyguanosine was prepared by enzymatic coupling of [4,5,6,8-(13)C4]8-hydroxyguanine to deoxyribose-1-phosphate. Samples of human urine (2 ml) were spiked with the labeled nucleoside (13 nmol) and subjected to solid phase extraction and reversed phase high performance liquid chromatography. The 8-hydroxy-2'-deoxyguanosine thus isolated was hydrolyzed by treatment with aqueous formic acid, and the resulting 8-hydroxyguanine was converted into its tetrakis-trimethylsilyl derivative and subjected to gas-liquid chromatographic-mass spectrometric analysis. Repeated determinations of 8-hydroxy-2'-deoxyguanosine in pools of urine showed coefficients of variation of 5 and 8% at concentrations of 8-hydroxy-2'-deoxyguanosine equal to 18 and 2 nM, respectively. Determination of 8-hydroxy-2'-deoxyguanosine in samples of urine spiked with different amounts of the unlabeled nucleoside showed a mean recovery of 102%. Application of the analytical method to a group of 11 apparently healthy subjects (mean age, 47 years) showed a mean level of endogenously produced 8-hydroxy-2'-deoxyguanosine equal to 1.33 +/- 0.29 micromol/mol creatinine. The level recorded for another group of 15 younger subjects (mean age, 28 years) was somewhat higher, that is, 1.58 +/- 0.84 micromol/mol creatinine, corresponding to a 24-h production rate of 8-hydroxy-2'-deoxyguanosine equal to 20.6 +/- 11.6 nmol (288 +/- 140 pmol/24 h x kg body weight). Hemochromatosis is a hereditary disease characterized by increased absorption of iron from the gastrointestinal tract and deposition of iron in organs. Application of the analytical method to a group of 12 patients with hereditary hemochromatosis who were under treatment with venesections showed a mean level of urinary 8-hydroxy-2'-deoxyguanosine equal to 1.39 +/- 0.40 micromol/mol creatinine. This value was not significantly different from those of healthy subjects. The fact that these patients had only slight or moderate iron overload at the time of urinary sample collection may have influenced the urinary levels of 8-hydroxy-2'-deoxyguanosine in the present study. PMID:9890648

  18. Accelerator mass spectrometry as a bioanalytical tool for nutritional research

    SciTech Connect

    Vogel, J.S.; Turteltaub, K.W.

    1997-09-01

    Accelerator Mass Spectrometry is a mass spectrometric method of detecting long-lived radioisotopes without regard to their decay products or half-life. The technique is normally applied to geochronology, but recently has been developed for bioanalytical tracing. AMS detects isotope concentrations to parts per quadrillion, quantifying labeled biochemicals to attomole levels in milligram- sized samples. Its advantages over non-isotopeic and stable isotope labeling methods are reviewed and examples of analytical integrity, sensitivity, specificity, and applicability are provided.

  19. Direct determination of methylmercury and inorganic mercury in biological materials by solid sampling-electrothermal vaporization-inductively coupled plasma-isotope dilution-mass spectrometry.

    PubMed

    Gelaude, I; Dams, R; Resano, M; Vanhaecke, F; Moens, L

    2002-08-01

    This paper reports on the use of solid sampling-electrothermal vaporization-inductively coupled plasma mass spectrometry (SS-EIV-ICPMS) for the direct and simultaneous determination of methylmercury and inorganic mercury in biological materials. The main advantage of this fast and sensitive method is that no sample preparation is required. In this way, the sample throughput can be considerably increased, problems of contamination and analyte losses are kept to a minimum and, even more important, the original chemical form of the different analyte species in the solid samples is preserved. To achieve this goal, a solid sample is inserted into a graphite furnace of the boat-in-tube type and is subsequently submitted to an appropriate temperature program, leading to the separate vaporization of methylmercury and inorganic mercury, which are transported into the ICP by means of an argon carrier gas. The separation was accomplished within 75 s. For the quantification of the two peaks, species-unspecific isotope dilution was used. For this purpose, a stable flow of argon loaded with gaseous Hg isotopically enriched in 200Hg was generated using a permeation tube that was constructed in-house. Its emission rate was determined by collecting the mercury released during a given time interval on a gold-coated silica absorber, after which the amount collected was released by heating of the absorber and determined by cold vapor atomic absorption spectrometry (CVAAS) and cold vapor atomic fluorescence spectrometry (CVAFS). A reference material from the Canadian National Research Council (NRC) (TORT-2) was used to assess the accuracy of the method. For the application of the method to samples with diverse mercury contents, the spike/sample ratio can be optimized by varying the emission rate of the permeation tube simply by adapting its temperature. To prove the feasibility of this approach, two reference materials (BCR 463 and DORM-2) with a methylmercury content more than 10 times higher than that of TORT-2 were also analyzed. The detection limits obtained for 1 mg of sample (2 ng g(-1) and 6 ng g(-1) for methylmercury and inorganic mercury, respectively) were found to be sufficiently low for this kind of application and are competitive when compared to other techniques. PMID:12175173

  20. Mass Spectrometry & Proteomics Services Unit

    E-print Network

    Fletcher, Robin

    Mass Spectrometry & Proteomics Services Unit Peptide and Protein Submission Form Website: http for analysis is dependent on sample complexity. Normally it takes 1-2 days for mass determination, and 3-5 days for protein identification by in-gel digestion and LC MS/MS analysis. 2. Mass spectrometric analysis Operator

  1. Linear electric field mass spectrometry

    DOEpatents

    McComas, David J. (Los Alamos, NM); Nordholt, Jane E. (Los Alamos, NM)

    1992-01-01

    A mass spectrometer and methods for mass spectrometry. The apparatus is compact and of low weight and has a low power requirement, making it suitable for use on a space satellite and as a portable detector for the presence of substances. High mass resolution measurements are made by timing ions moving through a gridless cylindrically symmetric linear electric field.

  2. Linear electric field mass spectrometry

    DOEpatents

    McComas, D.J.; Nordholt, J.E.

    1992-12-01

    A mass spectrometer and methods for mass spectrometry are described. The apparatus is compact and of low weight and has a low power requirement, making it suitable for use on a space satellite and as a portable detector for the presence of substances. High mass resolution measurements are made by timing ions moving through a gridless cylindrically symmetric linear electric field. 8 figs.

  3. A World without Sample Preparation: Developing Rapid Uranium Isotope Measurement Capabilities by Resonance Ionization Mass Spectrometry (RIMS)

    SciTech Connect

    Knight, K B; Hutcheon, I D; Isselhardt, B H; Savina, M R; Prussin, S G

    2009-06-08

    We are developing highly sensitive, highly discriminating laser-based techniques for rapid determination of isotopic compositions. Rapid command of such information is critical to assessment of the origin and history of nuclear materials, particularly in post-detonation scenarios.

  4. Validation of the determination of the B isotopic composition in Roman glasses with laser ablation multi-collector inductively coupled plasma-mass spectrometry

    NASA Astrophysics Data System (ADS)

    Devulder, Veerle; Gerdes, Axel; Vanhaecke, Frank; Degryse, Patrick

    2015-03-01

    The applicability of laser ablation multi-collector inductively coupled plasma-mass spectrometry (LA-MC-ICP-MS) for the determination of the B isotopic composition in Roman glasses was investigated. The ?11B values thus obtained provide information on the natron flux used during the glass-making process. The glass samples used for this purpose were previously characterized using pneumatic nebulization (PN) MC-ICP-MS. Unfortunately, this method is time-consuming and labor-intensive and consumes some 100 mg of sample, which is a rather high amount for ancient materials. Therefore, the use of the less invasive and faster LA-MC-ICP-MS approach was explored. In this work, the results for 29 Roman glasses and 4 home-made glasses obtained using both techniques were compared to assess the suitability of LA-MC-ICP-MS in this context. The results are in excellent agreement within experimental uncertainty. No difference in overall mass discrimination was observed between the Roman glasses, NIST SRM 610 reference glass and B6 obsidian. The expanded uncertainty of the LA-MC-ICP-MS approach was estimated to be < 2‰, which is similar to that obtained upon sample digestion and PN-MC-ICP-MS measurement.

  5. Characterization and quantification of histidine degradation in therapeutic protein formulations by size exclusion-hydrophilic interaction two dimensional-liquid chromatography with stable-isotope labeling mass spectrometry.

    PubMed

    Wang, Chunlei; Chen, Sike; Brailsford, John A; Yamniuk, Aaron P; Tymiak, Adrienne A; Zhang, Yingru

    2015-12-24

    Two dimensional liquid chromatography (2D-LC) coupling size exclusion (SEC) and hydrophilic interaction chromatography (HILIC) is demonstrated as a useful tool to study polar excipients, such as histidine and its degradant, in protein formulation samples. The SEC-HILIC setup successfully removed interferences from complex sample matrices and enabled accurate mass measurement of the histidine degradation product, which was then determined to be trans-urocanic acid. Because the SEC effluent is a strong solvent for the second dimension HILIC, experimental parameters needed to be carefully chosen, i.e., small transferring loop, fast gradient at high flow rates for the second dimension gradient, in order to mitigate the solvent mismatch and to ensure good peak shapes for HILIC separations. In addition, the generation of trans-urocanic acid was quantified by single heart-cutting SEC-HILIC 2D-LC combined with stable-isotope labeling mass spectrometry. Compared with existing 2D quantification methods, the proposed approach is fast, insensitive to solvent mismatch between dimensions, and tolerant of small retention time shifts in the first dimension. Finally, the first dimension diode array detector was found to be a potential degradation source for photolabile analytes such as trans-urocanic acid. PMID:26674608

  6. Mass spectrometry. [in organic chemistry

    NASA Technical Reports Server (NTRS)

    Burlingame, A. L.; Shackleton, C. H. L.; Howe, I.; Chizhov, O. S.

    1978-01-01

    A review of mass spectrometry in organic chemistry is given, dealing with advances in instrumentation and computer techniques, selected topics in gas-phase ion chemistry, and applications in such fields as biomedicine, natural-product studies, and environmental pollution analysis. Innovative techniques and instrumentation are discussed, along with chromatographic-mass spectrometric on-line computer techniques, mass spectral interpretation and management techniques, and such topics in gas-phase ion chemistry as electron-impact ionization and decomposition, photoionization, field ionization and desorption, high-pressure mass spectrometry, ion cyclotron resonance, and isomerization reactions of organic ions. Applications of mass spectrometry are examined with respect to bio-oligomers and their constituents, biomedically important substances, microbiology, environmental organic analysis, and organic geochemistry.

  7. Measurement of ?18O, ?17O, and 17O-excess in water by off-axis integrated cavity output spectroscopy and isotope ratio mass spectrometry.

    PubMed

    Berman, Elena S F; Levin, Naomi E; Landais, Amaelle; Li, Shuning; Owano, Thomas

    2013-11-01

    Stable isotopes of water have long been used to improve understanding of the hydrological cycle, catchment hydrology, and polar climate. Recently, there has been increasing interest in measurement and use of the less-abundant (17)O isotope in addition to (2)H and (18)O. Off-axis integrated cavity output spectroscopy (OA-ICOS) is demonstrated for accurate and precise measurements ?(18)O, ?(17)O, and (17)O-excess in liquid water. OA-ICOS involves no sample conversion and has a small footprint, allowing measurements to be made by researchers collecting the samples. Repeated (514) high-throughput measurements of the international isotopic reference water standard Greenland Ice Sheet Precipitation (GISP) demonstrate the precision and accuracy of OA-ICOS: ?(18)OVSMOW-SLAP = -24.74 ± 0.07‰ (1?) and ?(17)OVSMOW-SLAP = -13.12 ± 0.05‰ (1?). For comparison, the International Atomic Energy Agency (IAEA) value for ?(18)OVSMOW-SLAP is -24.76 ± 0.09‰ (1?) and an average of previously reported values for ?(17)OVSMOW-SLAP is -13.12 ± 0.06‰ (1?). Multiple (26) high-precision measurements of GISP provide a (17)O-excessVSMOW-SLAP of 23 ± 10 per meg (1?); an average of previously reported values for (17)O-excessVSMOW-SLAP is 22 ± 11 per meg (1?). For all these OA-ICOS measurements, precision can be further enhanced by additional averaging. OA-ICOS measurements were compared with two independent isotope ratio mass spectrometry (IRMS) laboratories and shown to have comparable accuracy and precision as the current fluorination-IRMS techniques in ?(18)O, ?(17)O, and (17)O-excess. The ability to measure accurately ?(18)O, ?(17)O, and (17)O-excess in liquid water inexpensively and without sample conversion is expected to increase vastly the application of ?(17)O and (17)O-excess measurements for scientific understanding of the water cycle, atmospheric convection, and climate modeling among others. PMID:24032448

  8. Mass fractionation processes of transition metal isotopes

    NASA Astrophysics Data System (ADS)

    Zhu, X. K.; Guo, Y.; Williams, R. J. P.; O'Nions, R. K.; Matthews, A.; Belshaw, N. S.; Canters, G. W.; de Waal, E. C.; Weser, U.; Burgess, B. K.; Salvato, B.

    2002-06-01

    Recent advances in mass spectrometry make it possible to utilise isotope variations of transition metals to address some important issues in solar system and biological sciences. Realisation of the potential offered by these new isotope systems however requires an adequate understanding of the factors controlling their isotope fractionation. Here we show the results of a broadly based study on copper and iron isotope fractionation during various inorganic and biological processes. These results demonstrate that: (1) naturally occurring inorganic processes can fractionate Fe isotope to a detectable level even at temperature ˜1000°C, which challenges the previous view that Fe isotope variations in natural system are unique biosignatures; (2) multiple-step equilibrium processes at low temperatures may cause large mass fractionation of transition metal isotopes even when the fractionation per single step is small; (3) oxidation-reduction is an importation controlling factor of isotope fractionation of transition metal elements with multiple valences, which opens a wide range of applications of these new isotope systems, ranging from metal-silicate fractionation in the solar system to uptake pathways of these elements in biological systems; (4) organisms incorporate lighter isotopes of transition metals preferentially, and transition metal isotope fractionation occurs stepwise along their pathways within biological systems during their uptake.

  9. Online gas chromatography combustion/pyrolysis-isotope ratio mass spectrometry (HRGC-C/P-IRMS) of (+/-)-Dihydroactinidiolide from tea ( Camellia sinensis ) and rooibos tea ( Aspalathus linearis ).

    PubMed

    del Mar Caja, María; Preston, Christina; Menzel, Michael; Kempf, Michael; Schreier, Peter

    2009-07-01

    Online capillary gas chromatography-isotope ratio mass spectrometry in both the combustion and the pyrolysis modes (HRGC-C/P-IRMS) was employed to perform authentication studies of the flavoring agent (+/-)-dihydroactinidiolide. Thus, the delta(13)C(V-PDB) and delta(2)H(V-SMOW) values of synthetic (ex synthetic beta-ionone and natural beta-carotene) as well as enzymatically (ex synthetic and natural beta-carotene) produced references were studied in comparison with those of the natural substance isolated from black (n = 17) and green teas (n = 6) ( Camellia sinensis ) as well as Rooibos tea ( Aspalathus linearis ) (n = 7). The isotope values determined for both the synthetic and enzymatically produced samples of (+/-)-dihydroactinidiolide reflected the influence of the origin of their educts. Hence, in cases when synthetic educts were used, the delta(13)C(V-PDB) and delta(2)H(V-SMOW) values ranged from -27.0 to -28.4 per thousand and from -28 to -169 per thousand, respectively, whereas the use of natural educts led to ranges from -30.3 to -31.6 per thousand and from -154 to -228 per thousand, respectively. As to the tea samples, delta(13)C(V-PDB) and delta(2)H(V-SMOW) values ranging from -29.0 to -34.1 per thousand and from -153 to -274 per thousand, respectively, were recorded for (+/-)-dihydroactinidiolide from black and green teas, whereas that from Rooibos tea showed (2)H/(1)H ratios ranging from -189 to -210 per thousand as well as slightly enriched values in the (13)C/(12)C ratios ranging from -24.4 to -27.1 per thousand. PMID:19514730

  10. Validation of an isotope dilution gas chromatography-mass spectrometry method for combined analysis of oxysterols and oxyphytosterols in serum samples.

    PubMed

    Schött, Hans-Frieder; Lütjohann, Dieter

    2015-07-01

    We describe the validation of a method for the analysis of oxysterols, i.e. oxycholesterols and oxyphytosterols, in human serum using gas chromatography-mass spectrometry selected ion monitoring (GC-MS-SIM). Concentrations of 7?- and 7?-hydroxy-, and 7oxo-cholesterol, -campesterol, and -sitosterol as well as 4?-hydroxycholesterol and side-chain oxygenated 24S-, 25-, and 27-hydroxycholesterol were determined by isotope dilution methodology. After saponification at room temperature the oxysterols were extracted, separated from their substrates, cholesterol, campesterol, and sitosterol, by solid phase extraction, and subsequently derivatised to their corresponding trimethylsilyl-ethers prior to GC-MS-SIM. In order to prevent artificial autoxidation butylated hydroxytoluene and ethylenediaminetetraacetic acid were added. The validation of the method was performed according to the International Conference on Harmonisation guidance, including limits of detection and quantification, ranges, recovery and precision. Due to improved instrumental settings and work-up procedure, limits of detection and quantification ranged between 8.0-202.0pg/mL and 28.0-674pg/mL, respectively. Recovery data in five calibration points varied between 91.9% and 116.8% and in serum samples between 93.1% and 118.1%. The mean coefficient of variation (CV) for the recovery of all compounds was <10%. Well satisfying CVs for within-day precision (2.1-10.8%) and for between-day precision (2.3-12.1%) were obtained. More than 20 samples could be processed in a single routine day and test series of about 300 samples can be realised without impairment of the validation parameters during a sequence. Comparison of oxysterol and oxyphytosterol content in serum and plasma revealed no difference. A fully validated isotope dilution methodology for the quantification of oxycholesterols and oxyphytosterols from human serum or plasma is presented. PMID:25701095

  11. Measurement of (5'R)- and (5'S)-8,5'-cyclo-2'-deoxyadenosines in DNA in vivo by liquid chromatography/isotope-dilution tandem mass spectrometry

    SciTech Connect

    Jaruga, Pawel; Department of Clinical Biochemistry, Collegium Medicum, Nicolaus Copernicus University, Bydgoszcz ; Xiao, Yan; Nelson, Bryant C.; Dizdaroglu, Miral

    2009-09-04

    Oxidatively induced DNA lesions (5'R)- and (5'S)-8,5'-cyclo-2'-deoxyadenosines (R-cdA and S-cdA) are detectable and accumulate in vivo due to disease states and defects in DNA repair. They block transcription and inhibit gene expression, and may play a role in disease processes. Accurate measurement of these lesions in DNA in vivo is necessary to understand their biological effects. We report on a methodology using liquid chromatography/isotope-dilution tandem mass spectrometry to measure R-cdA and S-cdA in DNA. This methodology permitted the detection of these compounds at a level of 0.1 fmol on-column. Levels of R-cdA and S-cdA in mouse liver DNA amounted to 0.133 {+-} 0.024 and 0.498 {+-} 0.065 molecules/10{sup 7} DNA 2'-deoxynucleosides, respectively. The successful measurement of R-cdA and S-cdA in DNA in vivo suggests that this methodology will be used for understanding of their repair and biological consequences, and that these compounds may be used as putative biomarkers for disease states.

  12. Quantification of DNA damage products resulting from deamination, oxidation and reaction with products of lipid peroxidation by liquid chromatography isotope dilution tandem mass spectrometry

    PubMed Central

    Taghizadeh, Koli; McFaline, Jose L.; Pang, Bo; Sullivan, Matthew; Dong, Min; Plummer, Elaine; Dedon, Peter C.

    2009-01-01

    The analysis of damage products as biomarkers of inflammation has been hampered by a poor understanding of the chemical biology of inflammation, the lack of sensitive analytical methods, and a focus on single chemicals as surrogates for inflammation. To overcome these problems, we developed a general and sensitive liquid chromatographic tandem mass spectrometry (LC/MS-MS) method to quantify, in a single DNA sample, the nucleoside forms of seven DNA lesions reflecting the range of chemistries associated with inflammation: 2?-deoxyuridine, 2?-deoxyxanthosine, and 2?-deoxyinosine from nitrosative deamination; 8-oxo-2?-deoxyguanosine from oxidation; and 1,N2-etheno-2?-deoxyguanosine, 1,N6-etheno-2?-deoxyadenosine, and 3,N4-etheno-2?-deoxycytidine arising from reaction of DNA with lipid peroxidation products. Using DNA purified from cells or tissues under conditions that minimize artifacts, individual nucleosides are purified by HPLC and quantified by isotope-dilution, electrospray ionization LC/MS-MS. The method can be applied to other DNA damage products and requires 4-6 days to complete depending upon the number of samples. PMID:18714297

  13. Detection of FGF15 in plasma by stable isotope standards and capture by anti-peptide antibodies and targeted mass spectrometry.

    PubMed

    Katafuchi, Takeshi; Esterházy, Daria; Lemoff, Andrew; Ding, Xunshan; Sondhi, Varun; Kliewer, Steven A; Mirzaei, Hamid; Mangelsdorf, David J

    2015-06-01

    Fibroblast growth factor 15 (FGF15) has been proposed as a postprandial hormone that signals from intestine to liver to regulate bile acid and carbohydrate homeostasis. However, detecting FGF15 in blood using conventional techniques has proven difficult. Here, we describe a stable isotope standards and capture by anti-peptide antibodies (SISCAPA) assay that combines immuno-enrichment with selected reaction monitoring (SRM) mass spectrometry to overcome this issue. Using this assay, we show that FGF15 circulates in plasma in an FXR and circadian rhythm-dependent manner at concentrations that activate its receptor. Consistent with the proposed endocrine role for FGF15 in liver, mice lacking hepatocyte expression of the obligate FGF15 co-receptor, ?-Klotho, have increased bile acid synthesis and reduced glycogen storage despite having supraphysiological plasma FGF15 concentrations. Collectively, these data demonstrate that FGF15 functions as a hormone and highlight the utility of SISCAPA-SRM as a sensitive assay for detecting low-abundance proteins in plasma. PMID:26039452

  14. Studies on the analysis of 25-hydroxyvitamin D3 by isotope-dilution liquid chromatography–tandem mass spectrometry using enzyme-assisted derivatisation

    PubMed Central

    Abdel-Khalik, Jonas; Crick, Peter J.; Carter, Graham D.; Makin, Hugh L.; Wang, Yuqin; Griffiths, William J.

    2014-01-01

    The total serum concentration of 25-hydroxyvitamins D (25-hydroxyvitamin D3 and 25-hydroxyvitamin D2) is currently used as an indicator of vitamins D status. Vitamins D insufficiency is claimed to be associated with multiple diseases, thus accurate and precise reference methods for the quantification of 25-hydroxyvitamins D are needed. Here we present a novel enzyme-assisted derivatisation method for the analysis of vitamins D metabolites in adult serum utilising 25-[26,26,26,27,27,27-2H6]hydroxyvitamin D3 as the internal standard. Extraction of 25-hydroxyvitamins D from serum is performed with acetonitrile, which is shown to be more efficient than ethanol. Cholesterol oxidase is used to oxidize the 3?-hydroxy group in the vitamins D metabolites followed by derivatisation of the newly formed 3-oxo group with Girard P reagent. 17?-Hydroxysteroid dehydrogenase type 10 is shown to oxidize selectively the 3?-hydroxy group in the 3?-hydroxy epimer of 25-hydroxyvitamin D3. Quantification is achieved by isotope-dilution liquid chromatography–tandem mass spectrometry. Recovery experiments for 25-hydroxyvitamin D3 performed on adult human serum give recovery of 102–106%. Furthermore in addition to 25-hydroxyvitamin D3, 24,25-dihydroxyvitamin D3 and other uncharacterised dihydroxy metabolites, were detected in adult human serum. PMID:24486315

  15. Determination of Os by isotope dilution-inductively coupled plasma-mass spectrometry with the combination of laser ablation to introduce chemically separated geological samples

    NASA Astrophysics Data System (ADS)

    Sun, Yali; Ren, Minghao; Xia, Xiaoping; Li, Congying; Sun, Weidong

    2015-11-01

    A method was developed for the determination of trace Os in geological samples by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) with the combination of chemical separation and preconcentration. Samples are digested using aqua regia in Carius tubes, and the Os analyte is converted into volatile OsO4, which is distilled and absorbed with HBr. The HBr solution is concentrated for further Os purification using the microdistillation technique. The purified Os is dissolved in 10 ?l of 0.02% sucrose-0.005% H3PO4 solution and then evaporated on pieces of perfluoroalkoxy (PFA) film, resulting in the formation of a tiny object (< 3 × 104 ?m2 superficial area). Using LA-ICP-MS measurements, the object can give Os signals at least 100 times higher than those provided by routine solution-ICP-MS while successfully avoiding the memory effect. The procedural blank and detection limit in the developed technique are 3.0 pg and 1.8 pg for Os, respectively when 1 g of samples is taken. Reference materials (RM) are analyzed, and their Os concentrations obtained by isotope dilution are comparable to reference or literature values. Based on the individual RM results, the precision is estimated within the range of 0.6 to 9.4% relative standard deviation (RSD), revealing that this method is applicable to the determination of trace Os in geological samples.

  16. Characterization of diesel fuel by chemical separation combined with capillary gas chromatography (GC) isotope ratio mass spectrometry (IRMS).

    PubMed

    Harvey, Scott D; Jarman, Kristin H; Moran, James J; Sorensen, Christina M; Wright, Bob W

    2012-09-15

    The purpose of this study was to perform a preliminary investigation of compound-specific isotope analysis (CSIA) of diesel fuels to evaluate whether the technique could distinguish diesel samples from different sources/locations. The ability to differentiate or correlate diesel samples could be valuable for discovering fuel tax evasion schemes or for environmental forensic studies. Two urea adduction-based techniques were used to isolate the n-alkanes from the fuel. Both carbon isotope ratio (?(13)C) and hydrogen isotope ratio (?D) values for the n-alkanes were then determined by CSIA in each sample. The samples investigated had ?(13)C values that ranged from -30.1‰ to -26.8‰, whereas ?D values ranged from -83‰ to -156‰. Plots of ?D versus ?(13)C with sample n-alkane points connected in order of increasing carbon number gave well-separated clusters with characteristic shapes for each sample. Principal components analysis (PCA) with ?(13)C, ?D, or combined ?(13)C and ?D data was applied to extract the maximum information content. PCA scores plots could clearly differentiate the samples, thereby demonstrating the potential of this approach for distinguishing (e.g., fingerprinting) fuel samples using ?(13)C and ?D values. PMID:22967550

  17. Qualitative Metabolome Analysis of Human Cerebrospinal Fluid by 13C-/12C-Isotope Dansylation Labeling Combined with Liquid Chromatography Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Guo, Kevin; Bamforth, Fiona; Li, Liang

    2011-02-01

    Metabolome analysis of human cerebrospinal fluid (CSF) is challenging because of low abundance of metabolites present in a small volume of sample. We describe and apply a sensitive isotope labeling LC-MS technique for qualitative analysis of the CSF metabolome. After a CSF sample is divided into two aliquots, they are labeled by 13C-dansyl and 12C-dansyl chloride, respectively. The differentially labeled aliquots are then mixed and subjected to LC-MS using Fourier-transform ion cyclotron resonance mass spectrometry (FTICR MS). Dansylation offers significant improvement in the performance of chromatography separation and detection sensitivity. Moreover, peaks detected in the mass spectra can be readily analyzed for ion pair recognition and database search based on accurate mass and/or retention time information. It is shown that about 14,000 features can be detected in a 25-min LC-FTICR MS run of a dansyl-labeled CSF sample, from which about 500 metabolites can be profiled. Results from four CSF samples are compared to gauge the detectability of metabolites by this method. About 261 metabolites are commonly detected in replicate runs of four samples. In total, 1132 unique metabolite ion pairs are detected and 347 pairs (31%) matched with at least one metabolite in the Human Metabolome Database. We also report a dansylation library of 220 standard compounds and, using this library, about 85 metabolites can be positively identified. Among them, 21 metabolites have never been reported to be associated with CSF. These results illustrate that the dansylation LC-FTICR MS method can be used to analyze the CSF metabolome in a more comprehensive manner.

  18. Imaging mass spectrometry in microbiology

    PubMed Central

    Watrous, Jeramie D.; Dorrestein, Pieter C.

    2013-01-01

    Mass spectrometry tools which allow for the 2-D visualization of the distribution of trace metals, metabolites, surface lipids, peptides and proteins directly from biological samples without the need for chemical tagging or antibodies are becoming increasingly useful for microbiology applications. These tools, comprised of different imaging mass spectrometry techniques, are ushering in an exciting new era of discovery by allowing for the generation of chemical hypotheses based on of the spatial mapping of atoms and molecules that can correlate to or transcend observed phenotypes. In this review, we explore the wide range of imaging mass spectrometry techniques available to microbiologists and describe their unique applications to microbiology with respect to the types of microbiology samples to be investigated. PMID:21822293

  19. Symposium on accelerator mass spectrometry

    SciTech Connect

    1981-01-01

    The area of accelerator mass spectrometry has expanded considerably over the past few years and established itself as an independent and interdisciplinary research field. Three years have passed since the first meeting was held at Rochester. A Symposium on Accelerator Mass Spectrometry was held at Argonne on May 11-13, 1981. In attendance were 96 scientists of whom 26 were from outside the United States. The present proceedings document the program and excitement of the field. Papers are arranged according to the original program. A few papers not presented at the meeting have been added to complete the information on the status of accelerator mass spectrometry. Individual papers were prepared separately for the data base.

  20. Ion Mobility Spectrometry (IMS) and Mass Spectrometry

    SciTech Connect

    Shvartsburg, Alexandre A.

    2010-04-20

    In a media of finite viscosity, the Coulomb force of external electric field moves ions with some terminal speed. This dynamics is controlled by “mobility” - a property of the interaction potential between ions and media molecules. This fact has been used to separate and characterize gas-phase ions in various modes of ion mobility spectrometry (IMS) developed since 1970. Commercial IMS devices were introduced in 1980-s for field detection of volatile traces such as explosives and chemical warfare agents. Coupling to soft-ionization sources, mass spectrometry (MS), and chromatographic methods in 1990-s had allowed IMS to handle complex samples, enabling new applications in biological and environmental analyses, nanoscience, and other areas. Since 2003, the introduction of commercial systems by major instrument vendors started bringing the IMS/MS capability to broad user community. The other major development of last decade has been the differential IMS or “field asymmetric waveform IMS” (FAIMS) that employs asymmetric time-dependent electric field to sort ions not by mobility itself, but by the difference between its values in strong and weak electric fields. Coupling of FAIMS to conventional IMS and stacking of conventional IMS stages have enabled two-dimensional separations that dramatically expand the power of ion mobility methods.

  1. Mass spectrometry for biomarker development

    SciTech Connect

    Wu, Chaochao; Liu, Tao; Baker, Erin Shammel; Rodland, Karin D.; Smith, Richard D.

    2015-06-19

    Biomarkers potentially play a crucial role in early disease diagnosis, prognosis and targeted therapy. In the past decade, mass spectrometry based proteomics has become increasingly important in biomarker development due to large advances in technology and associated methods. This chapter mainly focuses on the application of broad (e.g. shotgun) proteomics in biomarker discovery and the utility of targeted proteomics in biomarker verification and validation. A range of mass spectrometry methodologies are discussed emphasizing their efficacy in the different stages in biomarker development, with a particular emphasis on blood biomarker development.

  2. Measurement of ?18O, ?17O, and 17O-excess by Off-Axis Integrated Cavity Output Spectroscopy and Isotope Ratio Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Berman, E. S.; Levin, N.; Landais, A.; Li, S.; Owano, T. G.

    2013-12-01

    Water stable isotopes have for many years been used to study the hydrological cycle, catchment hydrology, and polar climate. Recently, there has been mounting interest in measurement and use of the less-abundant 17O isotope in addition to 2H and 18O. Off-axis integrated cavity output spectroscopy (OA-ICOS) measures ?18O, ?17O, and 17O-excess in liquid water without sample preparation or highly-trained operators. OA-ICOS allows measurements to be made on a relatively compact and affordable instrument by researchers collecting the samples. Numerous (514) high-throughput measurements of the international water standard GISP are used to demonstrate the precision and accuracy of OA-ICOS: ?18O =-24.74 × 0.06 ‰ (HWHM) and ?17O = -13.12 × 0.04 ‰ (HWHM). For comparison, the IAEA value for ?18O of GISP is 24.76 × 0.09 ‰ (1?) and an average of previously reported values for ?17O of GISP is -13.12 × 0.06 ‰ (1?). Repeated (26) high-precision measurements of GISP provide a 17O-excess of 23 × 9 per meg (HWHM); an average of previously reported values for 17O-excess is 22 × 11 per meg (1?). The precision of OA-ICOS measurements of ?18O, ?17O, and 17O-excess can be further enhanced by additional averaging. Comparison with two independent isotope ratio mass spectrometry (IRMS) laboratories shows that OA-ICOS has equivalent accuracy and precision as the current fluorination-IRMS techniques in ?18O, ?17O, and 17O-excess. The capability to accurately measure ?18O, ?17O, and 17O-excess in liquid water inexpensively and without sample preparation is expected to enhance both the number and breadth of applications of ?17O and 17O-excess for understanding of the water cycle, atmospheric convection, and climate modeling among others. 17O-excess measurement accuracy demonstrated by measurements of GISP and four commercially-available USGS standards by OA-ICOS and two independent IRMS labs. Error bars represent one standard error of the mean. The line behind the GISP columns shows the collected average of 3 previously reported IRMS measurements.

  3. Relative Quantification of Carboxylic Acid Metabolites by Liquid-Chromatography Mass-Spectrometry Using Isotopic Variants of Cholamine

    PubMed Central

    Lamos, Shane M.; Shortreed, Michael R.; Frey, Brian L.; Belshaw, Peter J.; Smith, Lloyd M.

    2008-01-01

    Labeling reagents that differ only in their isotopic composition offer a powerful approach to achieve relative quantification between samples by ESI-MS. Heavy and light isotopic forms of cholamine, which contain a positively charged quaternary ammonium group, were synthesized and tested as new labeling reagents for the relative quantification of carboxylic acid-containing metabolites, specifically fatty acids. The positive charge on cholamine ensures that the labeled product is also positively charged under all LC/MS conditions, regardless of mobile phase pH. This leads to high ionization efficiency and correspondingly high detection sensitivity, demonstrated here for the analysis of fatty acids in positive ion mode ESI-MS after reverse-phase separation under acidic conditions. Good accuracy and precision were obtained by mixing heavy- and light-labeled hydrolyzed egg lipid extracts in different known ratios. The relative quantification results for ten observed fatty acids had an average absolute error of 4.6% and an average coefficient of variation (CV) of 2.6%. The labeling strategy yielded a median CV of 6% when employed for fatty acid analysis of eggs from chickens fed various dietary supplements. PMID:17563114

  4. Characterization of Diesel Fuel by Chemical Separation Combined with Capillary Gas Chromatography (GC) Isotope Ratio Mass Spectrometry (IRMS)

    SciTech Connect

    Harvey, Scott D.; Jarman, Kristin H.; Moran, James J.; Sorensen, Christina M.; Wright, Bob W.

    2011-09-15

    The purpose of this study was to perform a preliminary investigation of compound-specific isotope analysis (CSIA) of diesel fuels to evaluate whether the technique could distinguish between the diesel samples from different sources/locations. The ability to differentiate or correlate diesel samples could be valuable for detecting fuel tax evasion schemes. Two fractionation techniques were used to isolate the n-alkanes from the fuel. Both ?13C and ?D values for the n-alkanes were then determined by CSIA in each sample. Plots of ?D versus ?13C with sample n-alkane points connected in order of increasing carbon number gave well separated clusters with characteristic shapes for each sample. Principal components analysis (PCA) with ?13C, ?D, or combined ?13C and ?D data on the yielded scores plots that could clearly differentiate the samples, thereby demonstrating the potential of this approach for fingerprinting fuel samples using the ?13C and ?D values.

  5. Determination of 4(5)-methylimidazole in carbonated beverages by isotope-dilution liquid chromatography-tandem mass spectrometry.

    PubMed

    Ratnayake, Geemitha; Halldorson, Thor; Bestvater, Lianna; Tomy, Gregg T

    2015-01-01

    The purpose of this study was to develop a method to quantify 4(5)-methylimidazole (4-MEI), a suspected carcinogen, in carbonated beverages by simple sample dilution and isotope-dilution reverse-phase LC-MS/MS. Isotope dilution using hexa-deuterated methylimidazole (d6-4-MEI) was used to quantify native 4-MEI and to assess matrix effects quantitatively. The accuracy of the method was assessed by intentionally fortifying a negative control sample at three doses: low, medium and high (replicates of n = 5 each) with a known amount of 4-MEI. The respective absolute error in each case was 18.7 ± 0.7%, 14.6 ± 2.8% and 21.1 ± 9.7%. Within-day (intra-) and day-to-day (inter-) repeatability, determined as the relative standard deviation by fortifying a negative control sample (n = 5), were 9.5% and 15.4%, respectively. Average ion suppression of d6-4-MEI in beer was 63.9 ± 3.2%, while no suppression or enhancement was seen in non-alcoholic samples. The instrument and method limit of detection were calculated as 0.6 and 5.8 ng ml(-1), respectively. 4(5)-Methylimidazole was quantified in a variety of store-bought consumer beverages and it was found that in many of the samples tested consuming a single can of beer would result in intake levels of 4-MEI that exceed the no significant risk guideline of 29 µg day(-1). Conversely, 4-MEI in the samples was orders of magnitude smaller than the European Food Safety Authority acceptable daily intake threshold value of 100 mg kg(-1) bw day(-1). PMID:25994392

  6. High-precision measurements of uranium and thorium isotopic ratios by multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS)

    NASA Astrophysics Data System (ADS)

    Wang, Lisheng; Ma, Zhibang; Duan, Wuhui

    2015-04-01

    Isotopic compositions of U-Th and 230Th dating have been widely used in earth sciences, such as chronology, geochemistry, oceanography and hydrology. In this study, five ages of different carbonate samples were measured using 230Th dating technique with U-Th high-precision isotopic measurements by multi-collector inductively coupled plasma mass spectrometry, in Uranium-series Chronology Laboratory, Institute of Geology and Geophysics, Chinese Academy of Sciences.In this study, the precision and accuracy of uranium isotopic composition were estimated by measuring the uranium ratios of NBS-CRM 112A, NBS-CRM U500 and HU-1. The mean measured ratios, 234U/238U = 52.86 (±0.04) × 10-6 and ?234U = -38.36 (±0.77) × 10-3 for NBS-CRM 112A, 234U/238U = 10.4184 (±0.0001) × 10-3, 236U/238U = 15.43 (±0.01) × 10-4 and 238U/235U = 1.00021 (±0.00002) for NBS-CRM U500, 234U/238U = 54.911 (±0.007) and ?234U = -1.04 (±0.13) × 10-3 for HU-1 (95% confidence levels). The U isotope data for standard reference materials are in excellent agreement with previous studies, further highlighting the reliability and analytical capabilities of our technique. We measured the thorium isotopic ratios of three different thorium standards by MC-ICPMS. The three standards (Th-1, Th-2 and Th-3) were mixed by HU-1 and NBS 232Th standard, with the 230Th/232Th ratios from 10-4 to 10-6. The mean measured atomic ratios, 230Th/232Th = 2.1227 (±0.0024) × 10-6, 2.7246 (±0.0026) × 10-5, and 2.8358 (±0.0007) × 10-4 for Th-1, Th-2 and Th-3 (95% confidence levels), respectively. Using this technique, the following standard samples were dated by MC-ICPMS. Sample RKM-4, collected from Babardos Kendal Hill terrace, was used during the first stage of the Uranium-Series Intercomparison Project (USIP-I). Samples 76001, RKM-5 and RKM-6 were studied during the second stage of the USIP program (USIP-II). Sample 76001 is a laminated flowstone, collected from Sumidero Terejapa, Chiapas, Mexico, and samples RKM-5 and RKM-6 are from the Babardos III terrace and the lower terrace (6 to 10m) of Curacao, respectively. China RCM GBW04412 was also analyzed. The ages of the five standard samples mentioned above are 197970±1590 yr BP, 47520±220 yr BP, 129300±650 yr BP, 130830±550 yr BP, and 86940±300 yr BP for samples RKM-4, 76001, RKM-5, RKM-6 and GBW04412, respectively. The results are consistent with the data of the same samples analyzed in Institute of Global Environmental Change, Xi'an Jiaotong University and Department of Earth Sciences, University of Minnesota, USA within errors, which suggests that the technique in our lab is reliable.

  7. Gold assay with Knudsen effusion mass spectrometry

    NASA Astrophysics Data System (ADS)

    Bardi, U.; Niccolai, F.; Tosti, M.; Tolstogouzov, A.

    2008-06-01

    Commercial 18 carat (ct) gold alloys along with pure coinage metals have been studied with Knudsen effusion mass spectrometry. Isotopic fractionation in vapour phase and the enthalpies of vaporization were estimated for Au, Ag and Cu samples. The assaying of the gold content was carried out by means of calibration with respect to standard reference alloys measured with energy dispersive X-ray spectroscopy. The accuracy of the gold determination resulted of about 1.5 wt.[per mille sign] in the ternary Au-Ag-Cu alloy.

  8. Electrospray Ionization Mass Spectrometry

    SciTech Connect

    Kelly, Ryan T.; Marginean, Ioan; Tang, Keqi

    2014-06-13

    Electrospray Ionization (ESI) is a process whereby gas phase ions are created from molecules in solution. As a solution exits a narrow tube in the presence of a strong electric field, an aerosol of charged droplets are is formed that produces gas phase ions as they it desolvates. ESI-MS comprises the creation of ions by ESI and the determination of their mass to charge ratio (m/z) by MS.

  9. Studies on the analysis of 25-hydroxyvitamin D{sub 3} by isotope-dilution liquid chromatography–tandem mass spectrometry using enzyme-assisted derivatisation

    SciTech Connect

    Abdel-Khalik, Jonas; Crick, Peter J.; Carter, Graham D.; Makin, Hugh L.; Wang, Yuqin; Griffiths, William J.

    2014-04-11

    Highlights: • New method for the analysis of 25-hydroxyvitamin D{sub 3} exploiting Girard P derivatisation. • Method also applicable to vitamin D{sub 3}, 1?,25- and 24,25-dihydroxyvitamin D{sub 3}. • By modification of the method 3-epi-25-hydroxyvitamin D{sub 3} can also be analysed. - Abstract: The total serum concentration of 25-hydroxyvitamins D (25-hydroxyvitamin D{sub 3} and 25-hydroxyvitamin D{sub 2}) is currently used as an indicator of vitamins D status. Vitamins D insufficiency is claimed to be associated with multiple diseases, thus accurate and precise reference methods for the quantification of 25-hydroxyvitamins D are needed. Here we present a novel enzyme-assisted derivatisation method for the analysis of vitamins D metabolites in adult serum utilising 25-[26,26,26,27,27,27-{sup 2}H{sub 6}]hydroxyvitamin D{sub 3} as the internal standard. Extraction of 25-hydroxyvitamins D from serum is performed with acetonitrile, which is shown to be more efficient than ethanol. Cholesterol oxidase is used to oxidize the 3?-hydroxy group in the vitamins D metabolites followed by derivatisation of the newly formed 3-oxo group with Girard P reagent. 17?-Hydroxysteroid dehydrogenase type 10 is shown to oxidize selectively the 3?-hydroxy group in the 3?-hydroxy epimer of 25-hydroxyvitamin D{sub 3}. Quantification is achieved by isotope-dilution liquid chromatography–tandem mass spectrometry. Recovery experiments for 25-hydroxyvitamin D{sub 3} performed on adult human serum give recovery of 102–106%. Furthermore in addition to 25-hydroxyvitamin D{sub 3}, 24,25-dihydroxyvitamin D{sub 3} and other uncharacterised dihydroxy metabolites, were detected in adult human serum.

  10. Hydrogen radical removal causes complex overlapping isotope patterns of aromatic carboxylic acids in negative-ion matrix-assisted laser desorption/ionization mass spectrometry.

    PubMed

    Yamagaki, Tohru; Watanabe, Takehiro

    2012-01-01

    We studied the ionization process of aromatic carboxylic acids, including ones with or without hydroxy groups in matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS), because many natural products, metabolites, and drags contain those structural units. In the actual experimental data, benzoic acid was ionized as only deprotonated molecule [M-H](-). In contrast, both of negative molecular ion M(-) and deprotonated molecule [M-H](-) were generated from 2-naphthoic acid and 2-anthracenecarboxylic acid, and the ratio of negative molecular ion to deprotonated molecule M(-)/[M-H](-) was increased in 2-anthracenecarboxylic acid. In addition, the ratio of 2-anthracenecarboxylic acid was much higher than those of 1- and 9-anthracenecarboxylic acids among the three isomers. Therefore, 2-substitution induced the generation of the negative molecular ion M(-), which can made us prediction of the substituted positions from their overlapping peak isotope patterns. 2,5-Dihydroxybenzoic acid (2,5-DHBA) showed two deprotonated molecules, [M-H](-) and [M-H*-H](-), which was generated from a neutral hydrogen radical (H*) removal from a phenolic hydroxy group. The deprotonated molecule [M-H*-H](-) of 2,5-DHBA was the most abundant among six DHBAs and three hydroxybenzoic acids (hBAs). This observation raises the possibility that such a property of 2,5-DHBA could be a clue to explain its highest efficiency as a MALDI matrix. The order of the hydrogen radical removal from the phenolic hydroxy groups was the 3-<4-?5-positions in the DHBAs, and the 3-<4-positions in hBAs. We can distinguish among six DHBA isomers and three hBA isomers from their spectral pattern around the deprotonated molecules [M-H*-H](-) and [M-H](-). The intra-molecular hydrogen bonding between 1-carboxy and 2-hydroxy groups was an important factor in hydrogen radical removal in the hydroxylbenzoic acids and dihydroxybenzoic acids. PMID:24349906

  11. Selenium speciation and bioavailability in biofortified products using species-unspecific isotope dilution and reverse phase ion pairing-inductively coupled plasma-mass spectrometry.

    PubMed

    Kirby, J K; Lyons, G H; Karkkainen, M P

    2008-03-12

    In some regions of the world, where the bioavailability of selenium (Se) in soil is low and/or declining (e.g., due to use of high-sulfur fertilizers), there is increased risk of adverse affects on animals and human health. In recent years, increased research attention has focused on understanding the relationships between Se contents in foods and supplements and their nutritional benefits for animal and humans. The objective of this study was to use a species-unspecific isotope dilution and reverse phase ion pairing-inductively coupled plasma-mass spectrometry techniques for the identification and quantification of Se species in biofortified grains (i.e., wheat and triticale), flour, and wheat biscuits. The information on Se species was used to gain an understanding of the bioavailability of Se in biofortified and process-fortified wheat biscuits used in a clinical trail. The major Se species identified in biofortified and process-fortified samples were selenomethionine (76-85%) and selenomethionine selenoxide (51-60%), respectively. Total plasma Se concentrations in the biofortified Se exposure group were found to increase throughout the 6 month trial period (mean=122 microg L(-1) at 0 months to 194 microg L(-1) at 6 months). In contrast, the trial group exposed to process-fortified Se biscuits showed little increase in mean total Se plasma concentrations until 4 months of exposure (mean=122 microg L(-1) at 0 months to 140 microg L(-1) at 4 months) that remained constant until the end of the trial period (mean=140 microg L(-1) at 4 months to 138 microg L(-1) at 6 months). The difference in total Se plasma concentrations may be due to the presence and bioavailability of different Se species in biofortified and process-fortified biscuits. An understanding of Se speciation in foods enables better understanding of pathways and their potential benefits for animals and humans. PMID:18254593

  12. Development and validation of a stable-isotope dilution liquid chromatography-tandem mass spectrometry method for the determination of bisphenols in ready-made meals.

    PubMed

    Regueiro, Jorge; Wenzl, Thomas

    2015-10-01

    Due to their growing consumption, ready-made meals are a major dietary component for many people in today's society, representing an important potential route of human exposure to several food contaminants. The recent restrictions in the use of bisphenol A have led the plastic industry to look for alternative chemicals, most of them belonging to the same family of p,p'-bisphenols. The aim of the current work was to develop and validate a method based on stable-isotope dilution liquid chromatography-tandem mass spectrometry for the analysis of bisphenol A and its main analogs - bisphenol S, 4,4'-sulfonylbis(2-methylphenol), bisphenol F, bisphenol E, bisphenol B, bisphenol Z, bisphenol AF, bisphenol AP, tetrabromobisphenol A and bisphenol P - in solid foodstuffs, and particularly in ready-made meals. Extraction was carried out by ultrasound-assisted extraction after sample disruption with sand. A selective solid-phase extraction procedure was then applied to reduce potential matrix interferences. Derivatization of bisphenols with pyridine-3-sulfonyl chloride increased their ionization efficiency by electrospray ionization. Validation of the proposed method was performed in terms of selectivity, matrix effects, linearity, precision, measurement uncertainty, trueness and limits of detection. Satisfactory repeatability and intermediate precision were obtained; the related relative standard deviations were ?7.8% and ?10%, respectively. The relative expanded uncertainty (k=2) was below 17% for all bisphenol analogs and the trueness of the method was demonstrated by spike recovery experiments. Low limits of detection, in the range from 0.025?gkg(-1) to 0.140?gkg(-1), were obtained for all compounds. To demonstrate the applicability of the proposed method, it was eventually applied to several ready-made meals purchased from different supermarkets in Belgium. PMID:26456223

  13. Detection of triclocarban and two co-contaminating chlorocarbanilides in US aquatic environments using isotope dilution liquid chromatography tandem mass spectrometry

    SciTech Connect

    Sapkota, Amir; Heidler, Jochen; Halden, Rolf U. . E-mail: rhalden@jhsph.edu

    2007-01-15

    The antimicrobial compound triclocarban (TCC; 3,4,4'-trichlorocarbanilide; CAS-bar 101-20-2) is a high-production-volume chemical, recently suggested to cause widespread contamination of US water resources. To test this hypothesis, we developed an isotope dilution liquid chromatography electrospray ionization tandem mass spectrometry method for ultratrace analysis of TCC (0.9ng/L detection limit) and analyzed low-volume water samples (200mL) along with primary sludge samples from across the United States. All river water samples (100%) collected downstream of wastewater treatment plants had detectable levels of TCC, as compared to 56% of those taken upstream. Concentrations of TCC (mean+/-standard deviation) downstream of sewage treatment plants (84+/-110ng/L) were significantly higher (P<0.05; Wilcoxon rank sum test) than those of samples taken upstream (12+/-15ng/L). Compared to surface water, mean TCC concentrations found in dried, primary sludge obtained from municipal sewage treatment plants in five states were six orders of magnitude greater (19,300+/-7100{mu}g/kg). Several river samples contained a co-contaminant, identified based on its chromatographic retention time, molecular base ion, and MS/MS fragmentation behavior as 4,4'-dichlorocarbanilide (DCC; CAS-bar 1219-99-4). In addition to TCC and DCC, municipal sludge contained a second co-contaminant, 3,3',4,4'-tetrachlorocarbanilide (TetraCC; CAS-bar 4300-43-0). Both newly detected compounds were present as impurities (0.2%{sub w/w} each) in technical grade TCC (99%). Application of the new method for chlorocarbanilide analysis yielded TCC occurrence data for 13 US states, confirmed the role of sewage treatment plants as environmental inputs of TCC, and identified DCC and TetraCC as previously unrecognized pollutants released into the environment alongside TCC.

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

    PubMed

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

    2015-07-01

    A method has been developed for the direct determination of agmatine in bacterial culture supernatants using isotope dilution ultra performance liquid chromatography (UPLC)-tandem mass spectrometry (UPLC-MS/MS). Agmatine determination in bacterial supernatants is comprised of spiking culture or isolate supernatants with a fixed concentration of uniformly labeled (13)C5,(15)N4-agmatine (synthesized by decarboxylation of uniformly labeled (13)C6,(15)N4-arginine using arginine decarboxylase from Pseudomonas aeruginosa) as an internal standard, followed by derivatization with 4-fluoro-7-nitro-2,1,3-benzoxadiazole (NBDF) to improve the reversed-phase chromatographic retention characteristics of agmatine, as well as the selectivity and sensitivity of UPLC-MS/MS detection of this amine in complex biologically derived mixtures. Intrasample precisions for measurement of agmatine in culture supernatants average 4.1% (relative standard deviation). Calibration curves are linear over the range 5 nM to 10 ?M, and the detection limit is estimated at 1.5 nM. To demonstrate the utility of the method, agmatine levels in supernatants of overnight cultures of wild-type (UCBPP-PA14), as well as arginine decarboxylase and agmatine deiminase mutant strains of P. aeruginosa strain UCBPP-PA14 were measured. This method verified that the mutant strains are lacking the specific metabolic capabilities to produce and metabolize agmatine. In addition, measurement of agmatine in supernatants of a panel of clinical isolates from patients with cystic fibrosis revealed that three of the P. aeruginosa isolates hyper-secreted agmatine into the supernatant, hypothesized to be a result of a mutation in the aguA gene. Because agmatine has potential inflammatory activities in the lung, this phenotype may be a virulence factor for P. aeruginosa in the lung environment of cystic fibrosis patients. PMID:25957842

  15. MASS SPECTROMETRY-BASED METABOLOMICS

    PubMed Central

    Dettmer, Katja; Aronov, Pavel A.; Hammock, Bruce D.

    2007-01-01

    This review presents an overview of the dynamically developing field of mass spectrometry-based metabolomics. Metabolomics aims at the comprehensive and quantitative analysis of wide arrays of metabolites in biological samples. These numerous analytes have very diverse physico-chemical properties and occur at different abundance levels. Consequently, comprehensive metabolomics investigations are primarily a challenge for analytical chemistry and specifically mass spectrometry has vast potential as a tool for this type of investigation. Metabolomics require special approaches for sample preparation, separation, and mass spectrometric analysis. Current examples of those approaches are described in this review. It primarily focuses on metabolic fingerprinting, a technique that analyzes all detectable analytes in a given sample with subsequent classification of samples and identification of differentially expressed metabolites, which define the sample classes. To perform this complex task, data analysis tools, metabolite libraries, and databases are required. Therefore, recent advances in metabolomics bioinformatics are also discussed. PMID:16921475

  16. Thin-layer chromatography/direct analysis in real time time-of-flight mass spectrometry and isotope dilution to analyze organophosphorus insecticides in fatty foods.

    PubMed

    Kiguchi, Osamu; Oka, Kazuko; Tamada, Masafumi; Kobayashi, Takashi; Onodera, Jun

    2014-11-28

    To assess food safety emergencies caused by highly hazardous chemical-tainted foods, simultaneous analysis of organophosphorus insecticides in fatty foods such as precooked foods was conducted using thin-layer chromatography/direct analysis in real time time-of-flight mass spectrometry (TLC/DART-TOFMS) and isotope dilution technique. Polar (methamidophos and acephate) and nonpolar organophosphorus insecticides (fenitrothion, diazinon, and EPN) were studied. Experiments to ascertain chromatographic patterns using TLC/DART-TOFMS reveal that it was more useful than GC/MS or GC/MS/MS for the simultaneous analyses of polar and nonpolar pesticides, while obviating the addition of a protective agent for tailing effects of polar pesticides. Lower helium gas temperature (260°C) for DART-TOFMS was suitable for the simultaneous analysis of target pesticides. Linearities were achieved respectively at a lower standard concentration range (0.05-5 ?g) for diazinon and EPN and at a higher standard concentration range (2.5-25 ?g) for methamidophos, acephate, and fenitrothion. Their respective coefficients of determination were ? 0.9989 and ? 0.9959. A few higher repeatabilities (RSDs) for diazinon and EPN were found (>20%), although isotope dilution technique was used. Application to the HPTLC plate without an automatic TLC sampler might be inferred as a cause of their higher RSDs. Detection limits were estimated in the higher picogram range for diazinon and EPN, and in the lower nanogram range for methamidophos, acephate, and fenitrothion. Aside from methamidophos, recovery results (n=3) obtained using a highly insecticide-tainted fatty food (dumpling) and raw food (grapefruit) samples (10mg/kg) using TLC/DART-TOFMS with both complex and simpler cleanups were not as susceptible to matrix effects (95-121%; RSD, 1.3-14%) as those using GC/MS/MS (102-117%; RSD, 0.4-8.5%), although dumpling samples using GC/MS were remarkably susceptible to matrix effects. The coupled method of TLC with simpler cleanup and DART-TOFMS can be regarded as the same analytical tool as GC/MS/MS, which is useful to assess food safety emergencies caused by highly hazardous chemical-tainted foods. PMID:25454149

  17. Determination of 135Cs by accelerator mass spectrometry

    NASA Astrophysics Data System (ADS)

    MacDonald, C. M.; Charles, C. R. J.; Zhao, X.-L.; Kieser, W. E.; Cornett, R. J.; Litherland, A. E.

    2015-10-01

    The ratio of anthropogenic 135Cs and 137Cs isotopes is characteristic of a uranium fission source. This research evaluates the technique of isotope dilution (yield tracing) for the purpose of quantifying 135Cs by accelerator mass spectrometry with on-line isobar separation. Interferences from Ba, Zn2, and isotopes of equal mass to charge ratios were successfully suppressed. However, some sample crosstalk from source contamination remains. The transmission and di-fluoride ionization efficiencies of Cs isotopes were found to be 8 × 10-3 and 1.7 × 10-7 respectively. This quantification of 135Cs using yield tracing by accelerator mass spectrometry shows promise for future environmental sample analysis once the issues of sample crosstalk and low efficiency can be resolved.

  18. Mass spectrometry of aerospace materials

    NASA Technical Reports Server (NTRS)

    Colony, J. A.

    1976-01-01

    Mass spectrometry is used for chemical analysis of aerospace materials and contaminants. Years of analytical aerospace experience have resulted in the development of specialized techniques of sampling and analysis which are required in order to optimize results. This work has resulted in the evolution of a hybrid method of indexing mass spectra which include both the largest peaks and the structurally significant peaks in a concise format. With this system, a library of mass spectra of aerospace materials was assembled, including the materials responsible for 80 to 90 percent of the contamination problems at Goddard Space Flight Center during the past several years.

  19. Sulfur Isotope Variation in Basaltic Melt Inclusions from Krakatau Revealed by a Newly Developed Secondary Ion Mass Spectrometry Technique for Silicate Glasses

    NASA Astrophysics Data System (ADS)

    Mandeville, C. W.; Shimizu, N.; Kelley, K. A.; Cheek, L.

    2008-12-01

    Sulfur is a ubiquitous element with variable valance states (S2-, S0, S4+, S6+) allowing for its participation in a wide variety of chemical and biogeochemical processes. However, its potential as an isotopic tracer in magmatic processes has not been fully developed and is crucial to understanding of sulfur recycling in subduction zones and between Earth's major reservoirs, mantle, lithosphere and coupled hydrosphere-atmosphere. Previous studies of silicate glasses and melt inclusions have been hampered by lack of an in situ isotopic measurement technique with spatial resolution of 10 to 100 microns. We have developed a new secondary ion mass spectrometry (SIMS) analytical technique for measurement of 34S/32S ratios in silicate glasses utilizing the IMS 1280 at Woods Hole Oceanographic Institution. A beam of 133Cs+ ions with 13 keV energy and current of 1-2 nA is focused onto a 10 micron spot and rastered over 30 × 30 microns. A Normal Incidence Electron Gun was used to compensate excess charge. The rastered beam is then centered to the optical axis of the machine, and a mechanical aperture is placed on the image plane to limit the area of analysis to the central 15 × 15 microns. The energy slit width was adjusted to 50 eV. A mass resolving power of 5500 was sufficient for eliminating mass interferences. A suite of synthetic and natural glasses with ?34SVCDT values spanning from - 5.6‰ to 18.5‰ with SiO2 from 44-72 weight % were measured. Magnitude of the instrumental mass fractionation (?) for 34S/32S ratios is 0.991 and is constant for all the glasses measured despite their compositions. Precision of individual measurements of 34S/32S ratios is 0.4 ‰, or better. Preliminary ?34S measurements of olivine-hosted basaltic melt inclusions in pre- 1883 basaltic scoria from Krakatau volcano Indonesia vary from -5.6 to 7.9‰ with sulfur concentrations from 490 to 2170 ppm, respectively. Host olivines are Fo77-80 and inclusions generally need minor to no post-entrapment corrections using KDFe-MgOl-liquid = 0.30. Most inclusions are basaltic though a few range up to basaltic andesite. Sulfur X-ray wavelength scans of melt inclusions indicates 60% of dissolved sulfur present as SO4. Dissolved H2O (by FTIR) ranges from 2.7 to 4.1 weight %, and CO2 concentrations are currently being determined. Dissolved Cl in melt inclusions ranges from 600 to 1100 ppm. Possible correlations of ?34S values with dissolved volatiles (by SIMS, and FTIR), and trace element concentrations are being evaluated.

  20. Computational mass spectrometry for small molecules

    PubMed Central

    2013-01-01

    The identification of small molecules from mass spectrometry (MS) data remains a major challenge in the interpretation of MS data. This review covers the computational aspects of identifying small molecules, from the identification of a compound searching a reference spectral library, to the structural elucidation of unknowns. In detail, we describe the basic principles and pitfalls of searching mass spectral reference libraries. Determining the molecular formula of the compound can serve as a basis for subsequent structural elucidation; consequently, we cover different methods for molecular formula identification, focussing on isotope pattern analysis. We then discuss automated methods to deal with mass spectra of compounds that are not present in spectral libraries, and provide an insight into de novo analysis of fragmentation spectra using fragmentation trees. In addition, this review shortly covers the reconstruction of metabolic networks using MS data. Finally, we list available software for different steps of the analysis pipeline. PMID:23453222

  1. Alpha spectrometry applications with mass separated samples.

    PubMed

    Dion, M P; Eiden, Gregory C; Iii, Orville T Farmer; Liezers, Martin; Robinson, John W

    2016-01-01

    (241)Am has been deposited using a novel technique that employs a commercial inductively coupled plasma mass spectrometer. This work presents results of high-resolution alpha spectrometry on the (241)Am samples using a small area passivated implanted planar silicon detector. We have also investigated the mass-based separation capability by developing a (238)Pu sample, present as a minor constituent in a (244)Pu standard, and performed subsequent radiometric counting. With this new sample development method, the (241)Am samples achieved the intrinsic energy resolution of the detector used for these measurements. There was no detectable trace of any other isotopes contained in the (238)Pu implant demonstrating the mass-based separation (or enhancement) attainable with this technique. PMID:26583262

  2. Quantification of polycyclic aromatic hydrocarbons based on comprehensive two-dimensional gas chromatography-isotope dilution mass spectrometry.

    PubMed

    Amador-Muñoz, Omar; Villalobos-Pietrini, Rafael; Aragón-Piña, Antonio; Tran, Tin C; Morrison, P; Marriott, Philip J

    2008-08-01

    Comprehensive two-dimensional gas chromatography (GCxGC) offers favourable resolution and sensitivity compared with conventional one-dimensional gas chromatography (1D-GC), as reported in many studies. These characteristics are of major interest when analytes are in trace concentration, and are present in complex mixtures, as is the case of polycyclic aromatic hydrocarbons (PAHs) in atmospheric particulate samples. Whilst GCxGC has been widely applied to identification of different types of analytes in several matrices, less seldom has it been used for quantification of these analytes. Although several quantitative methods have been proposed, they may be tedious and/or require considerable user development. Whereas quantification in 1D-GC is a routine and well-established procedure, in GCxGC, it is not so straightforward, especially where novel or untested procedures have yet to be incorporated into software packages. In the present study, it is proposed that a subset of the modulated peaks generated for each solute may be summed, based on the specific target ion mass of each compound present in a certified standard reference material (SRM) 1649a (urban dust). The ratio between a PAH and its corresponding deuterated (PAH-d) form showed that there is no statistical loss of sensitivity when this ratio is calculated based on whether the total sum of modulated peaks, or if only the two or the three most intense modulated peaks, are employed. Manual integration may be required, and here was found to give more acceptable values than automatic integration. Automated integration has been shown here to underestimate the modulated peak responses when low concentrations of PAHs were analyzed. Although for most PAHs good agreement with the certified values were observed, the analytical method needs to be further optimized for some of the other PAH, as can be see with those PAH with high variability in the range of urban dust analyzed. PMID:18620359

  3. Imaging Mass Spectrometry in Neuroscience

    PubMed Central

    2013-01-01

    Imaging mass spectrometry is an emerging technique of great potential for investigating the chemical architecture in biological matrices. Although the potential for studying neurobiological systems is evident, the relevance of the technique for application in neuroscience is still in its infancy. In the present Review, a principal overview of the different approaches, including matrix assisted laser desorption ionization and secondary ion mass spectrometry, is provided with particular focus on their strengths and limitations for studying different neurochemical species in situ and in vitro. The potential of the various approaches is discussed based on both fundamental and biomedical neuroscience research. This Review aims to serve as a general guide to familiarize the neuroscience community and other biomedical researchers with the technique, highlighting its great potential and suitability for comprehensive and specific chemical imaging. PMID:23530951

  4. RAPID COMMUNICATIONS IN MASS SPECTROMETRY Rapid Commun. Mass Spectrom. 2005; 19: 359362

    E-print Network

    Ehleringer, Jim

    ], respectively, by analyzing fifty 100 mL sam- ples filled from five cylinders with a [CO2] range of 275 mmol mol for stable isotope and concentration analyses of CO2 from small atmospheric samples Andrew J. Schauer, continuous-flow isotope ratio mass spectrometry (CF-IRMS) sys- tem for the analysis of d13 C, d18 O, and CO2

  5. Mass spectrometry. [review of techniques

    NASA Technical Reports Server (NTRS)

    Burlingame, A. L.; Kimble, B. J.; Derrick, P. J.

    1976-01-01

    Advances in mass spectrometry (MS) and its applications over the past decade are reviewed in depth, with annotated literature references. New instrumentation and techniques surveyed include: modulated-beam MS, chromatographic MS on-line computer techniques, digital computer-compatible quadrupole MS, selected ion monitoring (mass fragmentography), and computer-aided management of MS data and interpretation. Areas of application surveyed include: organic MS and electron impact MS, field ionization kinetics, appearance potentials, translational energy release, studies of metastable species, photoionization, calculations of molecular orbitals, chemical kinetics, field desorption MS, high pressure MS, ion cyclotron resonance, biochemistry, medical/clinical chemistry, pharmacology, and environmental chemistry and pollution studies.

  6. Standard test method for analysis of total and isotopic uranium and total thorium in soils by inductively coupled plasma-mass spectrometry

    E-print Network

    American Society for Testing and Materials. Philadelphia

    2008-01-01

    1.1 This test method covers the measurement of total uranium (U) and thorium (Th) concentrations in soils, as well as the determination of the isotopic weight percentages of 234U, 235U, 236U, and 238U, thereby allowing for the calculation of individual isotopic uranium activity or total uranium activity. This inductively coupled plasma-mass spectroscopy (ICP-MS) method is intended as an alternative analysis to methods such as alpha spectroscopy or thermal ionization mass spectroscopy (TIMS). Also, while this test method covers only those isotopes listed above, the instrumental technique may be expanded to cover other long-lived radioisotopes since the preparation technique includes the preconcentration of the actinide series of elements. The resultant sample volume can be further reduced for introduction into the ICP-MS via an electrothermal vaporization (ETV) unit or other sample introduction device, even though the standard peristaltic pump introduction is applied for this test method. The sample preparatio...

  7. A mass spectrometry primer for mass spectrometry imaging

    PubMed Central

    Rubakhin, Stanislav S.; Sweedler, Jonathan V.

    2011-01-01

    Mass spectrometry imaging (MSI), a rapidly growing subfield of chemical imaging, employs mass spectrometry (MS) technologies to create single- and multi-dimensional localization maps for a variety of atoms and molecules. Complimentary to other imaging approaches, MSI provides high chemical specificity and broad analyte coverage. This powerful analytical toolset is capable of measuring the distribution of many classes of inorganics, metabolites, proteins and pharmaceuticals in chemically and structurally complex biological specimens in vivo, in vitro, and in situ. The MSI approaches highlighted in this Methods in Molecular Biology volume provide flexibility of detection, characterization, and identification of multiple known and unknown analytes. The goal of this chapter is to introduce investigators who may be unfamiliar with MS to the basic principles of the mass spectrometric approaches as used in MSI. In addition to guidelines for choosing the most suitable MSI method for specific investigations, cross-references are provided to the chapters in this volume that describe the appropriate experimental protocols. PMID:20680583

  8. On-line monitoring of benzene air concentrations while driving in traffic by means of isotopic dilution gas chromatography/mass spectrometry.

    PubMed

    Davoli, E; Cappellini, L; Moggi, M; Ferrari, S; Fanelli, R

    1996-01-01

    There is no shortage of information about the average benzene concentrations in urban air, but there is very little about microenvironmental exposure, such as in-vehicle concentrations while driving in various traffic conditions, while refuelling, or while in a parking garage. The main reason for this lack of data is that no analytical instrumentation has been available to measure on-line trace amounts of benzene in such situations. We have recently proposed a highly accurate, high-speed cryofocusing gas chromatography/mass spectrometry (GC/MS) system for monitoring benzene concentrations in air. Accuracy of the analytical data is achieved by enrichment of the air sample before trapping, with a stable isotope permeation tube system. The same principles have been applied to a new instrument, specifically designed for operation on an electric vehicle (Ducato Elettra, Fiat). The zero emission vehicle and the fully transportable, battery-operated GC/MS system provide a unique possibility of monitoring benzene exposure in real everyday situations such as while driving, refuelling, or repairing a car. All power consumptions have been reduced so as to achieve a battery-operated GC/MS system. Liquid nitrogen cryofocusing has been replaced by a packed, inductively heated, graphitized charcoal microtrap. The instrument has been mounted on shock absorbers and installed in the van. The whole system has been tested in both fixed and mobile conditions. The maximum monitoring period without external power supply is 6 h. The full analytical cycle is 4 min, allowing close to real-time monitoring, and the minimum detectable level is 1 microgram/m3 for benzene. In-vehicle monitoring showed that, when recirculation was off and ventilation on, i.e., air from outside the vehicle was blown inside, concentrations varied widely in different driving conditions: moving from a parking lot into normal traffic on an urban traffic condition roadway yielded an increase in benzene concentration from 17 to 62.3 micrograms/m3 even if the actual distance was small. A larger increase was observed when a car was left with the engine running at a distance 2 m from the zero emission vehicle: We measured an increment of benzene concentrations from 15.2 to 174.4 micrograms/m3 with a car equipped with a catalytic converter, and from 19.1 to 386.3 micrograms/m3 with a car without such a converter. PMID:8738357

  9. Mass-independent isotope effects.

    PubMed

    Buchachenko, Anatoly L

    2013-02-28

    Three fundamental properties of atomic nuclei-mass, spin (and related magnetic moment), and volume-are the source of isotope effects. The mostly deserved and popular, with almost hundred-year history, is the mass-dependent isotope effect. The first mass-independent isotope effect which chemically discriminates isotopes by their nuclear spins and nuclear magnetic moments rather than by their masses was detected in 1976. It was named as the magnetic isotope effect because it is controlled by magnetic interaction, i.e., electron-nuclear hyperfine coupling in the paramagnetic species, the reaction intermediates. The effect follows from the universal physical property of chemical reactions to conserve angular momentum (spin) of electrons and nuclei. It is now detected for oxygen, silicon, sulfur, germanium, tin, mercury, magnesium, calcium, zinc, and uranium in a great variety of chemical and biochemical reactions including those of medical and ecological importance. Another mass-independent isotope effect was detected in 1983 as a deviation of isotopic distribution in reaction products from that which would be expected from the mass-dependent isotope effect. On the physical basis, it is in fact a mass-dependent effect, but it surprisingly results in isotope fractionation which is incompatible with that predicted by traditional mass-dependent effects. It is supposed to be a function of dynamic parameters of reaction and energy relaxation in excited states of products. The third, nuclear volume mass-independent isotope effect is detected in the high-resolution atomic and molecular spectra and in the extraction processes, but there are no unambiguous indications of its importance as an isotope fractionation factor in chemical reactions. PMID:23301791

  10. Diagnosing Prion Diseases: Mass Spectrometry-Based Approaches

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Mass spectrometry is an established means of quantitating the prions present in infected hamsters. Calibration curves relating the area ratios of the selected analyte peptides and their oxidized analogs to stable isotope labeled internal standards were prepared. The limit of detection (LOD) and limi...

  11. Utility of mass spectrometry in the diagnosis of prion diseases

    Technology Transfer Automated Retrieval System (TEKTRAN)

    We developed a sensitive mass spectrometry-based method of quantitating the prions present in a variety of mammalian species. Calibration curves relating the area ratios of the selected analyte peptides and their oxidized analogs to their homologous stable isotope labeled internal standards were pre...

  12. Calculation of Transactinide Homolog Isotope Production Reactions Possible with the Center for Accelerator Mass Spectrometry (CAMS) at Lawrence Livermore National Laboratory

    SciTech Connect

    Moody, K J; Shaughnessy, D A; Gostic, J M

    2011-11-29

    The LLNL heavy element group has been investigating the chemical properties of the heaviest elements over the past several years. The properties of the transactinides (elements with Z > 103) are often unknown due to their low production rates and short half-lives, which require lengthy cyclotron irradiations in order to make enough atoms for statistically significant evaluations of their chemistry. In addition, automated chemical methods are often required to perform consistent and rapid chemical separations on the order of minutes for the duration of the experiment, which can last from weeks to months. Separation methods can include extraction chromatography, liquid-liquid extraction, or gas-phase chromatography. Before a lengthy transactinide experiment can be performed at an accelerator, a large amount of preparatory work must be done both to ensure the successful application of the chosen chemical system to the transactinide chemistry problem being addressed, and to evaluate the behavior of the lighter elemental homologs in the same chemical system. Since transactinide chemistry is literally performed on one single atom, its chemical properties cannot be determined from bulk chemical matrices, but instead must be inferred from the behavior of the lighter elements that occur in its chemical group and in those of its neighboring elements. By first studying the lighter group homologs in a particular chemical system, when the same system is applied to the transactinide element under investigation, its decay properties can be directly compared to those of the homologues, thereby allowing an inference of its own chemistry. The Center for Accelerator Mass Spectrometry (CAMS) at Lawrence Livermore National Laboratory (LLNL) includes a 1 MV Tandem accelerator, capable of accelerating light ions such as protons to energies of roughly 15 MeV. By using the CAMS beamline, tracers of transactinide homolog elements can be produced both for development of chemical systems and for evaluation of homolog chemical properties. CAMS also offers an environment for testing these systems 'online' by incorporating automated chemical systems into the beamline so that tracers can be created, transported, and chemically separated all on the shorter timescales required for transactinide experiments. Even though CAMS is limited in the types and energies of ions they can accelerate, there are still a wide variety of reactions that can be performed there with commercially available target materials. The half-lives of these isotopes vary over a range that could be used for both online chemistry (where shorter half-lives are required) and benchtop tracers studies (where longer lived isotopes are preferred). In this document, they present a summary of tracer production reactions that could be performed at CAMS, specifically for online, automated chemical studies. They are from chemical groups four through seven, 13, and 14, which would be appropriate for studies of elements 104-107, 113, and 114. Reactions were selected that had (a) commercially available target material, (b) half-lives long enough for transport from a target chamber to an automated chemistry system, and (c) cross-sections at CAMS available projectile energies that were large enough to produce enough atoms to result in a statistically relevant signal after losses for transport and chemistry were considered. In addition, the resulting product atoms had to decay with an observable gamma-ray using standard Ge gamma-ray detectors. The table includes calculations performed for both metal targets and their corresponding oxides.

  13. Electrophoresis-mass spectrometry probe

    DOEpatents

    Andresen, B.D.; Fought, E.R.

    1987-11-10

    The invention involves a new technique for the separation of complex mixtures of chemicals, which utilizes a unique interface probe for conventional mass spectrometers which allows the electrophoretically separated compounds to be analyzed in real-time by a mass spectrometer. This new chemical analysis interface, which couples electrophoresis with mass spectrometry, allows complex mixtures to be analyzed very rapidly, with much greater specificity, and with greater sensitivity. The interface or probe provides a means whereby large and/or polar molecules in complex mixtures to be completely characterized. The preferred embodiment of the probe utilizes a double capillary tip which allows the probe tip to be continually wetted by the buffer, which provides for increased heat dissipation, and results in a continually operating interface which is more durable and electronically stable than the illustrated single capillary tip probe interface. 8 figs.

  14. Electrophoresis-mass spectrometry probe

    DOEpatents

    Andresen, Brian D. (Pleasanton, CA); Fought, Eric R. (Livermore, CA)

    1987-01-01

    The invention involves a new technique for the separation of complex mixtures of chemicals, which utilizes a unique interface probe for conventional mass spectrometers which allows the electrophoretically separated compounds to be analyzed in real-time by a mass spectrometer. This new chemical analysis interface, which couples electrophoresis with mass spectrometry, allows complex mixtures to be analyzed very rapidly, with much greater specificity, and with greater sensitivity. The interface or probe provides a means whereby large and/or polar molecules in complex mixtures to be completely characterized. The preferred embodiment of the probe utilizes a double capillary tip which allows the probe tip to be continually wetted by the buffer, which provides for increased heat dissipation, and results in a continually operating interface which is more durable and electronically stable than the illustrated single capillary tip probe interface.

  15. Resonance ionization mass spectrometry for precise measurements of iostope ratios.

    SciTech Connect

    Levine, J.; Savina, M. R.; Stephan, T.; Dauphas, N.; Davis, A. M.; Knight, K. B.; Pellin, M. J.; Materials Science Division; Chicago Center for Cosmochemistry; Univ.of Chicago; Univ. of California at Berkeley; LLNL

    2009-11-01

    Resonance ionization mass spectrometry offers extremely high sensitivity and elemental selectivity in microanalysis, but the isotopic precision attainable by this technique has been limited. Measured isotope ratios are sensitive to small fluctuations in the pointing, pulse timing, and wavelength of the resonance lasers. We show that, by minimizing these fluctuations using feedback controls and by power-broadening the optical transitions, we are able to measure chromium isotope ratios with statistics-limited precision better than 1%. Small additional improvements in reproducibility come from careful shaping of the electric field in the region where atoms are photoionized and from minimizing pulse-to-pulse variations in the time-of-flight mass spectrometer through which the photoions travel. The increased reproducibility of isotopic measurements on standard materials has enabled us to detect anomalous chromium isotopic abundances in presolar SiC grains extracted from primitive meteorites.

  16. Assessment of ultrasound-assisted extraction as sample pre-treatment for the measurement of lead isotope ratios in marine biological tissues by multicollector inductively coupled plasma-mass spectrometry

    NASA Astrophysics Data System (ADS)

    Costas-Rodríguez, M.; Lavilla, Isela; Bendicho, Carlos

    2011-06-01

    In this work, ultrasound-assisted extraction (UAE) was evaluated as a sample preparation procedure for lead isotope ratio measurements in marine biological tissues by multicollector inductively coupled plasma-mass spectrometry. 20 mg of marine biological tissue and 1 mL of acid extractant were sonicated for 3 min at 60% ultrasound amplitude. Matrix separation was performed in the supernatant using a chromatographic exchange resin (Sr-Spec™). Total elimination of organic matter was achieved during the separation step. Microwave-assisted digestion and dry-ashing were used for comparative purposes. No significant differences were found in lead isotope ratios at 95% of confidence level. UAE emerges as an advantageous alternative to classical methods for sample preparation owing to its simplicity and rapidity ( i.e. operation steps were reduced), low reagent consumption and low contamination risks.

  17. Analysis of household ignitable liquids and their post-combustion weathered residues using compound-specific gas chromatography-combustion-isotope ratio mass spectrometry.

    PubMed

    Schwartz, Zeland; An, Yan; Konstantynova, Kateryna I; Jackson, Glen P

    2013-12-10

    The continuing rise in home and vehicular arson cases involving the use of ignitable liquids continues to be an area of concern for criminal and civil investigators. In this study, the compound-specific ?(13)C values of various components of four flammable household chemicals were measured using a single quadrupole mass spectrometer and an isotope ratio mass spectrometer as simultaneous detectors for a gas chromatograph. Whereas compound-specific carbon isotope ratios were able to discriminate between different sources of neat (pre-combustion) ignitable liquids, analyses of the post-combustion residues were problematic. Weathering caused by combustion resulted in a significant increase in the (13)C content of specific peaks relative to the neat liquids (i.e. less negative delta values) such that the isotopic comparison of pre- and post-combustion residues resulted in fractionation ranging from 0 to +10‰. Because of the current lack of understanding of isotopic fractionation during combustion, and because of problems encountered with co-elution in the more complex samples, compound-specific IRMS does not appear to be suitable for fire debris analysis. The comparison of non-combusted or non-weathered ignitable liquids is much more reliable, especially for relatively simple mixtures, and is best suited for exclusionary purposes until such time as a comprehensive database of samples is developed. Without a measure of the population variance, one cannot presently predict the false positive identification rate for the comparison of two ignitable liquids; i.e. the probability that two random ignitable liquid samples have indistinguishable isotope ratios. PMID:24314542

  18. 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.

  19. A strategy for fast screening and identification of sulfur derivatives in medicinal Pueraria species based on the fine isotopic pattern filtering method using ultra-high-resolution mass spectrometry.

    PubMed

    Yang, Min; Zhou, Zhe; Guo, De-An

    2015-09-24

    Sulfurous compounds are commonly present in plants, fungi, and animals. Most of them were reported to possess various bioactivities. Isotopic pattern filter (IPF) is a powerful tool for screening compounds with distinct isotope pattern. Over the past decades, the IPF was used mainly to study Cl- and Br-containing compounds. To our knowledge, the algorithm was scarcely used to screen S-containing compounds, especially when combined with chromatography analyses, because the (34)S isotopic ion is drastically affected by (13)C2 and (18)O. Thus, we present a new method for a fine isotopic pattern filter (FIPF) based on the separated M + 2 ions ((12)Cx(1)Hy(16)Oz(32)S(13)C2(18)O, (12)Cx+2(1)Hy(16)Oz+1(34)S, tentatively named M + 2OC and M + 2S) with an ultra-high-resolution mass (100,000 FWHM @ 400 m/z) to screen sulfur derivatives in traditional Chinese medicines (TCM).This finer algorithm operates through convenient filters, including an accurate mass shift of M + 2OC and M + 2S from M and their relative intensity compared to M. The method was validated at various mass resolutions, mass accuracies, and screening thresholds of flexible elemental compositions. Using the established FIPF method, twelve S-derivatives were found in the popular medicinal used Pueraria species, and 9 of them were tentatively identified by high-resolution multiple stage mass spectrometry (HRMS(n)). The compounds were used to evaluate the sulfurous compounds' situation in commercially purchased Pueraria products. The strategy presented here provides a promising application of the IPF method in a new field. PMID:26423627

  20. Counting Molecules by Desorption Ionization and Mass Spectrometry/Mass Spectrometry.

    ERIC Educational Resources Information Center

    Cooks, R. G.; Busch, K. L.

    1982-01-01

    Discusses two newer methods in mass spectrometry and shows how they can increase signal and signal-to-noise ratios, respectively. The first method, desorption ionization (DI), increases sensitivity while the second method, mass spectrometry/mass spectrometry (MS/MS), increases specificity. Together, the two methods offer improved analytical…

  1. Detection of reactive metabolites using isotope-labeled glutathione trapping and simultaneous neutral loss and precursor ion scanning with ultra-high-pressure liquid chromatography triple quadruple mass spectrometry.

    PubMed

    Huang, Ke; Huang, Lingyi; van Breemen, Richard B

    2015-04-01

    Metabolic activation of drugs to electrophilic species is responsible for over 60% of black box warnings and drug withdrawals from the market place in the United States. Reactive metabolite trapping using glutathione (GSH) and analysis using high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) or HPLC with high resolution mass spectrometry (mass defect filtering) have enabled screening for metabolic activation to become routine during drug development. However, current MS-based approaches cannot detect all GSH conjugates present in complex mixtures, especially those present in extracts of botanical dietary supplements. To overcome these limitations, a fast triple quadrupole mass spectrometer-based approach was developed that can detect positively and negatively charged GSH conjugates in a single analysis without the need for advanced knowledge of the elemental compositions of potential conjugates and while avoiding false positives. This approach utilized UHPLC instead of HPLC to shorten separation time and enhance sensitivity, incorporated stable-isotope labeled GSH to avoid false positives, and used fast polarity switching electrospray MS/MS to detect GSH conjugates that form positive and/or negative ions. The general new method was then used to test the licorice dietary supplement Glycyrrhiza glabra, which was found to form multiple GSH conjugates upon metabolic activation. Among the GSH conjugates found in the licorice assay were conjugates with isoliquiritigenin and glabridin, which is an irreversible inhibitor of cytochrome P450 enzymes. PMID:25774910

  2. Development of a novel method for unraveling the origin of natron flux used in Roman glass production based on B isotopic analysis via multicollector inductively coupled plasma mass spectrometry.

    PubMed

    Devulder, Veerle; Degryse, Patrick; Vanhaecke, Frank

    2013-12-17

    The provenance of the flux raw material used in the manufacturing of Roman glass is an understudied topic in archaeology. Whether one or multiple sources of natron mineral salts were exploited during this period is still open for debate, largely because of the lack of a good provenance indicator. The flux is the major source of B in Roman glass. Therefore, B isotopic analysis of a sufficiently large collection and variety (origin and age) of such glass samples might give an indication of the number of flux sources used. For this purpose, a method based on acid digestion, chromatographic B isolation and B isotopic analysis using multicollector inductively coupled plasma mass spectrometry was developed. B isolation was accomplished using a combination of strong cation exchange and strong anion exchange chromatography. Although the B fraction was not completely matrix-free, the remaining Sb was shown not to affect the ?(11)B result. The method was validated using obsidian and archaeological glass samples that were stripped of their B content, after which an isotopic reference material with known B isotopic composition was added. Absence of artificial B isotope fractionation was demonstrated, and the total uncertainty was shown to be <2‰. A proof-of-concept application to natron glass samples showed a narrow range of ?(11)B, whereas first results for natron salt samples do show a larger difference in ?(11)B. These results suggest the use of only one natron source or of several sources with similar ?(11)B. This indicates that B isotopic analysis is a promising tool for the provenance determination of this flux raw material. PMID:24279483

  3. Advances in Chromatography, Mass Spectrometry & Lab Automation

    E-print Network

    Vertes, Akos

    #12;Advances in Chromatography, Mass Spectrometry & Lab Automation 2 Publisher's Note Kevin Davies&EN Media Group 4 Top Ten Chromatography, Mass Spectrometry, and Lab Automation Papers APPLICATION NOTES 10 Detection Of Methylmalonic Acid (MMA) In Plasma Using Hydro- philic Interaction Liquid Chromatography (HILIC

  4. S1 certification of alpha-endosulfan, beta-endosulfan, and endosulfan sulfate in a candidate certified reference material (organochlorine pesticides in tea) by isotope dilution gas chromatography-mass spectrometry.

    PubMed

    Sin, Della Wai-Mei; Wong, Yee-Lok; Cheng, Eddie Chung-Chin; Lo, Man-Fung; Ho, Clare; Mok, Chuen-Shing; Wong, Siu-Kay

    2015-04-01

    This paper presents the certification of alpha-endosulfan, beta-endosulfan, and endosulfan sulfate in a candidate tea certified reference material (code: GLHK-11-03) according to the requirements of the ISO Guide 30 series. Certification of GLHK-11-03 was based on an analytical method purposely developed for the accurate measurement of the mass fraction of the target analytes in the material. An isotope dilution mass spectrometry (IDMS) method involving determination by (i) gas chromatography-negative chemical ionization-mass spectrometry (GC-NCI-MS) and (ii) gas chromatography-electron ionization-high-resolution mass spectrometry (GC-EI-HRMS) techniques was employed. The performance of the described method was demonstrated through participation in the key comparison CCQM-K95 "Mid-Polarity Analytes in Food Matrix: Mid-Polarity Pesticides in Tea" organized by the Consultative Committee for Amount of Substance-Metrology in Chemistry in 2012, where the study material was the same as the certified reference material (CRM). The values reported by using the developed method were in good agreement with the key comparison reference value (KCRV) assigned for beta-endosulfan (727?±?14 ?g kg(-1)) and endosulfan sulfate (505?±?11 ?g kg(-1)), where the degree of equivalence (DoE) values were 0.41 and 0.40, respectively. The certified values of alpha-endosulfan, beta-endosulfan, and endosulfan sulfate in dry mass fraction in GLHK-11-03 were 350, 730, and 502 ?g kg(-1), respectively, and the respective expanded uncertainties, due to sample inhomogeneity, long-term and short-term stability, and variability in the characterization procedure, were 27 ?g kg(-1) (7.8 %), 48 ?g kg(-1) (6.6 %), and 33 ?g kg(-1) (6.6 %). PMID:25619984

  5. Elemental formula annotation of polar and lipophilic metabolites using (13) C, (15) N and (34) S isotope labelling, in combination with high-resolution mass spectrometry.

    PubMed

    Giavalisco, Patrick; Li, Yan; Matthes, Annemarie; Eckhardt, Aenne; Hubberten, Hans-Michael; Hesse, Holger; Segu, Shruthi; Hummel, Jan; Köhl, Karin; Willmitzer, Lothar

    2011-10-01

    The unbiased and comprehensive analysis of metabolites in any organism presents a major challenge if proper peak annotation and unambiguous assignment of the biological origin of the peaks are required. Here we provide a comprehensive multi-isotope labelling-based strategy using fully labelled (13) C, (15) N and (34) S plant tissues, in combination with a fractionated metabolite extraction protocol. The extraction procedure allows for the simultaneous extraction of polar, semi-polar and hydrophobic metabolites, as well as for the extraction of proteins and starch. After labelling and extraction, the metabolites and lipids were analysed using a high-resolution mass spectrometer providing accurate MS and all-ion fragmentation data, providing an unambiguous readout for every detectable isotope-labelled peak. The isotope labelling assisted peak annotation process employed can be applied in either an automated database-dependent or a database-independent analysis of the plant polar metabolome and lipidome. As a proof of concept, the developed methods and technologies were applied and validated using Arabidopsis thaliana leaf and root extracts. Along with a large repository of assigned elemental compositions, which is provided, we show, using selected examples, the accuracy and reliability of the developed workflow. PMID:21699588

  6. Chip-SIP: Stable Isotope Probing of RNA combining phylogenetic microarrays and Secondary Ion Mass Spectrometry (NanoSIMS) to link structure and function in microbial systems (Invited)

    NASA Astrophysics Data System (ADS)

    Mayali, X.; Weber, P. K.; Mabery, S.; Dekas, A.; Pett-Ridge, J.

    2013-12-01

    A primary goal of microbial ecology is to understand the biogeochemical role of individual microbial taxa in the environment. Our approach to tackle this challenge (Chip-SIP) involves the combination of high-density phylogenetic microarrays ('chips') and Stable Isotope Probing (SIP) to directly link identity and function. Microbial communities are incubated in the presence of substrate(s) enriched in 13C or 15N, RNA is extracted and hybridized onto a microarray synthesized on a conductive surface, and the array is analyzed with a NanoSIMS imaging mass spectrometer to quantify isotopic enrichment of individual probes. After testing the method with mixtures of stable isotope labeled laboratory isolates, we have investigated organic and inorganic carbon and nitrogen incorporation by microbial taxa in various ecosystems including San Francisco Bay, the coastal Pacific Ocean, California soils, and the hindguts of wood-eating beetles. We will summarize the methodology, describe the types of questions it has allowed us to investigate, and discuss some testable hypotheses about biogeochemical cycling in various environments that can benefit from this approach.

  7. Testing the limits of micro-scale analyses of Si stable isotopes by femtosecond laser ablation multicollector inductively coupled plasma mass spectrometry with application to rock weathering

    NASA Astrophysics Data System (ADS)

    Schuessler, Jan A.; von Blanckenburg, Friedhelm

    2014-08-01

    An analytical protocol for accurate in-situ Si stable isotope analysis has been established on a new second-generation custom-built femtosecond laser ablation system. The laser was coupled to a multicollector inductively coupled plasma mass spectrometer (fsLA-MC-ICP-MS). We investigated the influence of laser parameters such as spot size, laser focussing, energy density and repetition rate, and ICP-MS operating conditions such as ICP mass load, spectral and non-spectral matrix effects, signal intensities, and data processing on precision and accuracy of Si isotope ratios. We found that stable and reproducible ICP conditions were obtained by using He as aerosol carrier gas mixed with Ar/H2O before entering the plasma. Precise ?29Si and ?30Si values (better than ± 0.23‰, 2SD) can be obtained if the area ablated is at least 50 × 50 ?m; or, alternatively, for the analysis of geometric features down to the width of the laser spot (about 20 ?m) if an equivalent area is covered. Larger areas can be analysed by rastering the laser beam, whereas small single spot analyses reduce the attainable precision of ?30Si to ca. ± 0.6‰, 2SD, for < 30 ?m diameter spots. It was found that focussing the laser beam beneath the sample surface with energy densities between 1 and 3.8 J/cm2 yields optimal analytical conditions for all materials investigated here. Using pure quartz (NIST 8546 aka. NBS-28) as measurement standard for calibration (standard-sample-bracketing) did result in accurate and precise data of international reference materials and samples covering a wide range in chemical compositions (Si single crystal IRMM-017, basaltic glasses KL2-G, BHVO-2G and BHVO-2, andesitic glass ML3B-G, rhyolitic glass ATHO-G, diopside glass JER, soda-lime glasses NIST SRM 612 and 610, San Carlos olivine). No composition-dependent matrix effect was discernible within uncertainties of the method. The method was applied to investigate the Si isotope signature of rock weathering at the micro-scale in a corestone sampled from a highly weathered roadcut profile in the tropical Highlands of Sri Lanka. The results show that secondary weathering products accumulated in cracks and grain boundaries are isotopically lighter than their unweathered plagioclase host, consistent with isotopically heavy dissolved Si found in rivers.

  8. Statistical characterization of multiple-reaction monitoring mass spectrometry (MRM-MS) assays for quantitative proteomics

    E-print Network

    Mani, D R

    Multiple reaction monitoring mass spectrometry (MRM-MS) with stable isotope dilution (SID) is increasingly becoming a widely accepted assay for the quantification of proteins and peptides. These assays have shown great ...

  9. Standard test method for analysis of isotopic composition of uranium in nuclear-grade fuel material by quadrupole inductively coupled plasma-mass spectrometry

    E-print Network

    American Society for Testing and Materials. Philadelphia

    2000-01-01

    1.1 This test method is applicable to the determination of the isotopic composition of uranium (U) in nuclear-grade fuel material. The following isotopic weight percentages are determined using a quadrupole inductively coupled plasma-mass spectrometer (Q-ICP-MS): 233U, 234U, 235U, 236U, and 238U. The analysis can be performed on various material matrices after acid dissolution and sample dilution into water or dilute nitric (HNO3) acid. These materials include: fuel product, uranium oxide, uranium oxide alloys, uranyl nitrate (UNH) crystals, and solutions. The sample preparation discussed in this test method focuses on fuel product material but may be used for uranium oxide or a uranium oxide alloy. Other preparation techniques may be used and some references are given. Purification of the uranium by anion-exchange extraction is not required for this test method, as it is required by other test methods such as radiochemistry and thermal ionization mass spectroscopy (TIMS). This test method is also described i...

  10. Compact hydrogen/helium isotope mass spectrometer

    DOEpatents

    Funsten, Herbert O. (Los Alamos, NM); McComas, David J. (Los Alamos, NM); Scime, Earl E. (Morgantown, WV)

    1996-01-01

    The compact hydrogen and helium isotope mass spectrometer of the present invention combines low mass-resolution ion mass spectrometry and beam-foil interaction technology to unambiguously detect and quantify deuterium (D), tritium (T), hydrogen molecule (H.sub.2, HD, D.sub.2, HT, DT, and T.sub.2), .sup.3 He, and .sup.4 He concentrations and concentration variations. The spectrometer provides real-time, high sensitivity, and high accuracy measurements. Currently, no fieldable D or molecular speciation detectors exist. Furthermore, the present spectrometer has a significant advantage over traditional T detectors: no confusion of the measurements by other beta-emitters, and complete separation of atomic and molecular species of equivalent atomic mass (e.g., HD and .sup.3 He).

  11. Injection optics for fast mass switching for accelerator mass spectrometry

    NASA Astrophysics Data System (ADS)

    Weisser, D. C.; Fifield, L. K.; De Cesare, M.; Tims, S. G.; Lobanov, N. R.; Crook, G. G.; Tsifakis, D.; Tunningley, T. B.

    2013-04-01

    Accelerator Mass Spectrometry (AMS) measures the ratio of extremely small amounts of a radioactive isotope in the presence of ˜ 1015 times more stable ones. The isotopes are injected sequentially over a repeated period and observed at the exit of the accelerator. so any fluctuations in ion source output or transmission through the accelerator over a time comparable to the measurement time, will reduce the accuracy of such measurements. This compromise in accuracy can be lessened by reducing the switching time between isotopes from several seconds to a few milli-seconds. New AMS systems accomplish fast switching by modifying the beam energy though the 90 injection magnet by pulsing the voltage by several kV on the flight tube in the magnet. That requires that the flight tube be electrically insulated which competes with having the flight tube as large as possible. At the ANU, insulating the magnet flight tube would not only have reduced the acceptance of the injection system, but conflicted with a beam chopper attached to the flight tube, that would also have had to be insulated from the ground. This was not practical so the novel alternative of pulsing the voltage on the high voltage ion source deck is being implemented. Beam optics calculations have been performed and beam tests conducted that demonstrated that, in addition to pulsing the voltage on the 150 kV ion source deck, a pulsed Einzel lens in front of the following electrostatic quadrupole triplet lens is required to maintain isotope-independent transmission through the 14UD Pelletron accelerator. The high voltage rise time performance of the components of the system has been shown to be satisfactory.

  12. Quantification of N?-(2-Furoylmethyl)-L-lysine (furosine), N?-(Carboxymethyl)-L-lysine (CML), N?-(Carboxyethyl)-L-lysine (CEL) and total lysine through stable isotope dilution assay and tandem mass spectrometry.

    PubMed

    Troise, Antonio Dario; Fiore, Alberto; Wiltafsky, Markus; Fogliano, Vincenzo

    2015-12-01

    The control of Maillard reaction (MR) is a key point to ensure processed foods quality. Due to the presence of a primary amino group on its side chain, lysine is particularly prone to chemical modifications with the formation of Amadori products (AP), N?-(Carboxymethyl)-L-lysine (CML), N?-(Carboxyethyl)-L-lysine (CEL). A new analytical strategy was proposed which allowed to simultaneously quantify lysine, CML, CEL and the N?-(2-Furoylmethyl)-L-lysine (furosine), the indirect marker of AP. The procedure is based on stable isotope dilution assay followed by liquid chromatography tandem mass spectrometry. It showed high sensitivity and good reproducibility and repeatability in different foods. The limit of detection and the RSD% were lower than 5 ppb and below 8%, respectively. Results obtained with the new procedure not only improved the knowledge about the reliability of thermal treatment markers, but also defined new insights in the relationship between Maillard reaction products and their precursors. PMID:26041204

  13. Establishing Drug Resistance in Microorganisms by Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Demirev, Plamen A.; Hagan, Nathan S.; Antoine, Miquel D.; Lin, Jeffrey S.; Feldman, Andrew B.

    2013-08-01

    A rapid method to determine drug resistance in bacteria based on mass spectrometry is presented. In it, a mass spectrum of an intact microorganism grown in drug-containing stable isotope-labeled media is compared with a mass spectrum of the intact microorganism grown in non-labeled media without the drug present. Drug resistance is determined by predicting characteristic mass shifts of one or more microorganism biomarkers using bioinformatics algorithms. Observing such characteristic mass shifts indicates that the microorganism is viable even in the presence of the drug, thus incorporating the isotopic label into characteristic biomarker molecules. The performance of the method is illustrated on the example of intact E. coli, grown in control (unlabeled) and 13C-labeled media, and analyzed by MALDI TOF MS. Algorithms for data analysis are presented as well.

  14. Quantitative analysis of aberrant fatty acid composition of zebrafish hepatic lipids induced by organochlorine pesticide using stable isotope-coded transmethylation and gas chromatography-mass spectrometry.

    PubMed

    Zhong, Hongying; Dong, Linjie; Dong, Qingjian; Ke, Changshu; Fu, Jieying; Wang, Xiaoli; Liu, Cong; Dai, Ling

    2012-07-01

    Organochlorine pesticides have been extensively used worldwide for agricultural purposes. Due to their resistance to metabolism, a major public health concern has been raised. Aberrant hepatic lipid composition has been a hallmark of many liver diseases associated with exposure to various toxins and chemicals. And thus lots of efforts have been focused on the development of analytical techniques that can rapidly and quantitatively determine the changes in fatty acid composition of hepatic lipids. In this work, changes in fatty acid composition of hepatic lipids in response to DDT (dichlorodiphenyltrichloroethane) exposure were quantitatively analyzed by a gas chromatography-mass spectrometric approach based on stable isotope-coded transmethylation. It has been quantitatively demonstrated that polyunsaturated fatty acids including C20:3n3, C20:4n6, and C22:6n3 decrease in response to DDT exposure. However, saturated long chain fatty acids including C16:0, C18:0, as well as monounsaturated long chain fatty acid C18:1n9 consistently increase in a DDT-concentration-dependent manner. In particular, much higher changes in the level of hepatic C16:0 and C18:0 for male fish were observed than that for female fish. These experimental results are in accordance with qualitative histopathological analysis that revealed liver morphological alterations. The stable isotope-coded mass spectrometric approach provides a reliable means for investigating hepatotoxicity associated with fatty acid synthesis, desaturation, mitochondrial beta-oxidation, and lipid mobilization. It should be useful in elucidation of hepatotoxic mechanisms and safety assessment of environmental toxins. PMID:22648165

  15. [Determination of poppy ingredients in chafing dish materials by isotopic internal standard coupled with multiple reaction monitoring and online full scan mass spectrometry].

    PubMed

    Zhu, Weixia; Sun, Zhuanlian; Yuan, Ping; Yang, Jizhou; Liu, Yafeng; Sun, Wuyong

    2014-12-01

    A confirmative method was developed for determining five poppy alkaloids including morphine, codeine, papaverine, tibane, noscapine in chafing dish ingredients by high performance liquid chromatography coupled with triple quadrupole linear ion trap mass spectrometry (HPLC-Q Trap MS). The sample was extracted with dilute HCl solution under heating condition. The removal of lipid procedure was performed with hexane. The purification was carried out on a mixed-cation solid-phase extraction column (MCX) and ethyl acetate-methanol containing 5% aqueous ammonia was used for elution. A PAK ST column was used to separate the analytes, and 5 mmol/L ammonium acetate methanol and 10 mmol/L ammonium acetate (pH 3. 6) were used as mobile phases. The five alkaloids was detected in the positive mode simultaneously by multiple reaction monitoring (MRM) and online enhanced product ion full scan (EPI). The LODs were 0.05-0.5 µg/kg and the LOQs were 0. 2-2 µg/kg for the five poppy alkaloids. The overall recoveries of the method varied from 64. 2% to 110. 6%, and the RSD were between 4. 2% and 12. 5%. The EPI mass spectra of positive samples were searched through standard library for qualitative confirmation. The detection of real hot pot material samples showed this method can be used for the simple and accurate determination of the five poppy alkaloid residues in chafing dish. PMID:25902640

  16. Determination of bovine lactoferrin in dairy products by ultra-high performance liquid chromatography-tandem mass spectrometry based on tryptic signature peptides employing an isotope-labeled winged peptide as internal standard.

    PubMed

    Zhang, Jingshun; Lai, Shiyun; Cai, Zengxuan; Chen, Qi; Huang, Baifen; Ren, Yiping

    2014-06-01

    A new and sensitive determination method was developed for bovine lactoferrin in dairy products including infant formulas based on the signature peptide by ultra high-performance liquid chromatography and triple-quadrupole tandem mass spectrometry under the multiple reaction monitoring mode. The simple pretreatment procedures included the addition of a winged peptide containing the isotope-labeled signature peptide as internal standard, followed by an enzymatic digestion with trypsin. The signature peptide was chosen and identified from the tryptic hydrolyzates of bovine lactoferrin by ultra high-performance liquid chromatography and quadrupole-time-of-flight tandem mass spectrometry based on sequence database search. Analytes were separated on an ACQUITY UPLC BEH 300 C18 column and monitored by MS/MS in seven minutes. Quantitative result bias due to matrix effect and tryptic efficiency was corrected through the use of synthetic isotope-labeled standards. The limit of detection and limit of quantification were 0.3 mg/100 g and 1.0 mg/100 g, respectively. Bovine lactoferrin within the concentration range of 10-1000 nmol L(-1) showed a strong linear relationship with a linear correlation coefficient (r) of >0.998. The intra- and inter-day precision of the method were RSD<6.5% and RSD<7.1%, respectively. Excellent repeatability (RSD<6.4%) substantially supported the application of this method for the determination of bovine lactoferrin in dairy samples. The present method was successfully validated and applied to determination of bovine lactoferrin in dairy products including infant formulas. PMID:24856400

  17. The role of mass spectrometry in atomic weight determinations.

    PubMed

    De Laeter, John R

    2009-01-01

    The 1914 Nobel Prize for Chemistry was awarded to Theodore Richards, whose work provided an insight into the history of the birth and evolution of matter as embedded in the atomic weights. However, the secret to unlocking the hieroglyphics contained in the atomic weights is revealed by a study of the relative abundances of the isotopes. A consistent set of internationally accepted atomic weights has been a goal of the scientific community for over a century. Atomic weights were originally determined by chemical stoichiometry--the so-called "Harvard Method," but this methodology has now been superseded by the "physical method," in which the isotopic composition and atomic masses of the isotopes comprising an element are used to calculate the atomic weight with far greater accuracy than before. The role of mass spectrometry in atomic weight determinations was initiated by the discovery of isotopes by Thomson, and established by the pioneering work of Aston, Dempster, and Nier using sophisticated mass spectrographs. The advent of the sector field mass spectrometer in 1947, revolutionized the application of mass spectrometry for both solids and gases to other fields of science including atomic weights. Subsequently, technological advances in mass spectrometry have enabled atomic masses to be determined with an accuracy better than one part in 10(7), whilst the absolute isotopic composition of many elements has been determined to produce accurate values of their atomic weights. Conversely, those same technological developments have revealed significant variations in the isotope abundances of many elements caused by a variety of physiochemical mechanisms in natural materials. Although these variations were initially seen as an impediment to the accuracy with which atomic weights could be determined, it was quickly realized that nature had provided a new tool to investigate physiochemical and biogeochemical mechanisms in nature, which could be exploited by precise and accurate isotopic measurements. Atomic weights can no longer be regarded as constants of nature, except for the monoisotopic elements whose atomic weights are determined solely by the relative atomic mass of that nuclide. Stable isotope geochemists developed mass spectrometric protocols by the adoption of internationally accepted reference materials for the light elements, to which measurements from various laboratories could be compared. Subsequently, a number of heavy elements such as iron, molybdenum and cadmium have been shown to exhibit isotope fractionation. The magnitude of such isotope fractionation in nature is less than for the light elements, but technological developments, such as multiple collector-inductively coupled plasma-mass spectrometry, have enabled such fractionation effects to be determined. Measurements of the atomic weights of certain elements affect the determination of important fundamental constants such as the Avogadro Constant, the Faraday Constant and the Universal Gas Constant. Heroic efforts have been made to refine the accuracy of the atomic weight of silicon, with the objective of replacing the SI standard of mass--the kilogram--with the Avogadro Constant. Improvements in these fundamental constants in turn affect the set of self-consistent values of other basic constants through a least-squares adjustment methodology. Absolute isotope abundances also enable the Solar System abundances of the s-, r-, and p-process of nucleosynthesis to be accurately determined, thus placing constraints on theories of heavy element nucleosynthesis. Future developments in the science of atomic weight determinations are also examined. PMID:18785619

  18. Plasma Desorption Mass Spectrometry: Coming of Age.

    ERIC Educational Resources Information Center

    Cotter, Robert J.

    1988-01-01

    Discusses the history and development of Plasma Desorption Mass Spectrometry to determine molecular weights and structures of proteins and polymers. Outlines theory, instrumentation, and sample preparation commonly used. Gives several examples of resulting spectra. (ML)

  19. [Simultaneous determination of 7 female sex hormones in essential oil by high performance liquid chromatography-tandem mass spectrometry with isotope dilution].

    PubMed

    Huang, Baifen; Han, Zheng; Xu, Xiaomin; Cai, Zengxuan; Jiang, Wei; Ren, Yiping

    2011-01-01

    A reliable ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) method for the simultaneous determination of 7 female sex hormones (estriol, estradiol, estrone, ethinyloestradiol, dienestrol, hexestrol, diethylstilbestrol) in essential oil was developed. The sample was extracted by ethylacetate-normal hexane solution (2:98, v/v) and the extract was purified by a silica solid phase extraction-based clean-up column. Then, the analytes were separated on an ACQUITY UPLC BEH SHELD RP18 column (100 mm x 2.1 mm, 1.7 microm) in gradient elution with the mobile phases of water and acetonitrile. The separated compounds were detected with a Waters Xevo TQ MS tandem quadrupole mass spectrometer operated in negative electro-spray ionization using multiple reaction monitoring mode. Estriol-D3, estradiol-D3 and diethylstilbestrol-D6 were used as the internal standards to reduce the matrix effects. The limits of detection and quantitation for the 7 female sex hormones in essential oil were 0.3 -7 microg/kg and 1-20 microg/kg, respectively. Good linear relationships and high correlation coefficients (r2 > or = 0.997) were obtained in the mass concentration range of 20-500 microg/L. The average recoveries were 88.5%-114.8% and the intra-assay relative standard deviations were 4.8%-18.9% at the spiked levels of 20-500 microg/kg. Finally, a total of 12 samples randomly collected from different supermarkets in Zhejiang Province were screened for the 7 female sex hormones by the proposed method. The results showed that only one sample contained estradiol and estrone. PMID:21574395

  20. Comprehensive two-dimensional gas chromatography with isotope dilution time-of-flight mass spectrometry for the measurement of dioxins and polychlorinated biphenyls in foodstuffs. Comparison with other methods.

    PubMed

    Focant, Jean-François; Eppe, Gauthier; Scippo, Marie-Louise; Massart, Anne-Cécile; Pirard, Catherine; Maghuin-Rogister, Guy; De Pauw, Edwin

    2005-09-01

    A comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (GC x GC-TOF-MS) experimental setup was tested for the measurement of seven 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins (PCDDs), ten 2,3,7,8-substituted polychlorinated dibenzofurans (PCDFs), four non-ortho-polychlorinated biphenyls (PCBs), eight mono-ortho-PCBs, and six indicator PCBs (Aroclor 1260) in foodstuff samples. A 40m RTX-500 (0.18mm I.D., 0.10 microm df) was used as the first dimension (1D) and a 1.5 m BPX-50 (0.10mm I.D., 0.10 microm df) as the second dimension (2D). The GC x GC chromatographic separation was completed in 45 min. Quantification was performed using 13C-label isotope dilution (ID). Isotope ratios of the selected quantification ions were checked against theoretical values prior to peak assignment and quantification. The dynamic working range spanned three orders of magnitude. The lowest detectable amount of 2,3,7,8-TCDD was 0.2 pg. Fish, pork, and milk samples were considered. On a congener basis, the GC x GC-ID-TOF-MS method was compared to the reference GC-ID high resolution mass spectrometry (HRMS) method and to the alternative GC-ID tandem-in-time quadrupole ion storage mass spectrometry (QIST-MS/MS). PCB levels ranged from low picogram (pg) to low nanogram (ng) per gram of sample and data compared very well between the different methods. For all matrices, PCDD/Fs were at a low pg level (0.05-3 pg) on a fresh weight basis. Although congener profiles were accurately described, RSDs of GC x GC-ID-TOF-MS and GC-QIST-MS/MS were much higher than for GC-ID-HRMS, especially for low level pork and milk. On a toxic equivalent (TEQ) basis, all methods, including the dioxin-responsive chemically activated luciferase gene expression (DR-CALUX) assay, produced similar responses. A cost comparison is also presented. PMID:16130655

  1. Cadmium measurements in coral skeleton using isotope dilutioninductively coupled plasmamass spectrometry

    E-print Network

    Mcdonough, William F.

    Cadmium measurements in coral skeleton using isotope dilution­inductively coupled plasma for the precise analysis of Cd/Ca in coral skeleton using inductively coupled plasma­ mass spectrometry (ICP of a coral standard yielded a precision of ±2.2% (one standard deviation as a fraction of signal). Analyses

  2. Mono-isotope Prediction for Mass Spectra Using Bayes Network

    PubMed Central

    Li, Hui; Rwebangira, Mugizi Robert; Burge, Legand

    2015-01-01

    Mass spectrometry is one of the widely utilized important methods to study protein functions and components. The challenge of mono-isotope pattern recognition from large scale protein mass spectral data needs computational algorithms and tools to speed up the analysis and improve the analytic results. We utilized naïve Bayes network as the classifier with the assumption that the selected features are independent to predict mono-isotope pattern from mass spectrometry. Mono-isotopes detected from validated theoretical spectra were used as prior information in the Bayes method. Three main features extracted from the dataset were employed as independent variables in our model. The application of the proposed algorithm to publicMo dataset demonstrates that our naïve Bayes classifier is advantageous over existing methods in both accuracy and sensitivity. PMID:25620856

  3. Determination of Sr isotopes in calcium phosphates using laser ablation inductively coupled plasma mass spectrometry and their application to archaeological tooth enamel

    NASA Astrophysics Data System (ADS)

    Horstwood, M. S. A.; Evans, J. A.; Montgomery, J.

    2008-12-01

    The determination of accurate Sr isotope ratios in calcium phosphate matrices by laser ablation multi-collector ICP-MS is demonstrated as possible even with low Sr concentration archaeological material. Multiple on-line interference correction routines for doubly-charged REE, Ca dimers and Rb with additional calibration against TIMS-characterised materials are required to achieve this. The calibration strategy proposed uses both inorganic and biogenic apatite matrices to monitor and correct for a 40Ca- 31P- 16O polyatomic present at levels of 0.3-1% of the non-oxide peak, which interferes on 87Sr causing inaccuracies of 0.03-0.4% in the 87Sr/ 86Sr isotope ratio. The possibility also exists for synthetic materials to be used in this calibration. After correction for interferences total combined uncertainties of 0.04-0.15% (2SD) are achieved for analyses of 13-24 ?g of archaeological tooth enamel with Sr concentrations of ca. 100-500 ppm using MC-ICP-MS. In particular, for samples containing >300 ppm Sr, total uncertainties of ˜0.05% are possible utilising 7-12 ng Sr. Data quality is monitored by determination of 84Sr/ 86Sr ratios. When applied to an archaeological cattle tooth this approach shows Sr-isotope variations along the length of the tooth in agreement with independent TIMS data. The 40Ca- 31P- 16O polyatomic interference is the root cause of the bias at mass 87 during laser ablation ICP-MS analysis of inorganic and biogenic calcium phosphate (apatite) matrices. This results in inaccurate 87Sr/ 86Sr ratios even after correction of Ca dimers and doubly charged rare earth elements. This interference is essentially constant at specific ablation conditions and therefore the effect on 87Sr/ 86Sr data varies in proportion to changes in the Sr concentration of the ablated material. Complete elimination of this interference is unlikely through normal analytical mechanisms and therefore represents a limitation on the achievable accuracy of LA-(MC-)ICP-MS 87Sr/ 86Sr data without rigorous calibration to known reference materials.

  4. Tandem mass spectrometry: analysis of complex mixtures

    SciTech Connect

    Singleton, K.E.

    1985-01-01

    Applications of tandem mass spectrometry (MS/MS) for the analysis of complex mixtures results in increased specificity and selectivity by using a variety of reagent gases in both negative and positive ion modes. Natural isotopic abundance ratios were examined in both simple and complex mixtures using parent, daughter and neutral loss scans. MS/MS was also used to discover new compounds. Daughter scans were used to identify seven new alkaloids in a cactus species. Three of these alkaloids were novel compounds, and included the first simple, fully aromatic isoquinoline alkaloids reported in Cactaceae. MS/MS was used to characterize the chemical reaction products of coal in studies designed to probe its macromolecular structure. Negative ion chemical ionization was utilized to study reaction products resulting from the oxidation of coal. Possible structural units in the precursor coal were predicted based on the reaction products identified, aliphatic and aromatic acids and their anhydrides. The MS/MS method was also used to characterize reaction products resulting from coal liquefaction and/or extraction. These studies illustrate the types of problems for which MS/MS is useful. Emphasis has been placed on characterization of complex mixtures by selecting experimental parameters which enhance the information obtained. The value of using MS/MS in conjunction with other analytical techniques as well as the chemical pretreatment is demonstrated.

  5. 1912: a Titanic year for mass spectrometry.

    PubMed

    Downard, Kevin M

    2012-08-01

    The 1912 sinking of the Titanic continues to capture the imagination and fascination of the general public. The year coincides with the birth of mass spectrometry that began with the cathode ray experiments performed by Joseph John (J. J.) Thomson in Cambridge. Modifications made to Thomson's cathode ray apparatus by Francis William Aston, resulted in an increase in the brightness of the positive rays that aided their detection. This led to the discovery of heavy isotopes for many of the chemical elements in the ensuing decades. As the discovery of (22) Ne was reported in 1913, another of Thomson's students was taking part in an expedition to help save future ocean liners from the fate of the Titanic. Geoffrey Ingram Taylor took part in the first ice patrol of the North Atlantic in 1913 aboard the SS Scotia to investigate the formation and position of icebergs. This article, 100?years on, describes Taylor's work and its impact on safe ocean passage across the Atlantic. PMID:22899512

  6. Evaluation of the metabolic chiral inversion of d-selenomethionine in rats by stable isotope dilution gas chromatography-mass spectrometry.

    PubMed

    Matsukawa, Takehisa; Hasegawa, Hiroshi; Goto, Hitomi; Shinohara, Yoshihiko; Shinohara, Atsuko; Omori, Yuki; Ichida, Kimiyoshi; Yokoyama, Kazuhito

    2015-12-10

    The stereoselective pharmacokinetics of selenomethionine enantiomers in rats has been studied to evaluate the chiral inversion of d-selenomethionine to the l-enantiomer. After bolus intravenous administration of d- or l-selenomethionine to rats, the plasma concentrations of these two enantiomers were determined by stereoselective gas chromatography-mass spectrometry with selected ion monitoring. This method involved derivatization of selenomethionine enantiomers with HCl in methanol to form methyl ester followed by N-acylation with (+)-?-methoxy-?-trifluoromethylphenylacetyl chloride to form the diastereomeric amide, and separation of the diastereomer on GC with an achiral column. Plasma concentrations of administered d- and l-selenomethionine declined with terminal half-lives of 96±17min and 91±6min, respectively. l-Selenomethionine appeared rapidly in plasma after administration of d-selenomethionine, whereas d-selenomethionine was not detected in plasma after administration of l-selenomethionine. The fraction of conversion of d-selenomethionine to l-selenomethionine was estimated to be 61.3±14.5%. The present method evaluates the stereoselective pharmacokinetics of selenomethionine enantiomers, including the estimation of the metabolic chiral inversion. PMID:26001566

  7. Mass Spectrometry for Large Undergraduate Laboratory Sections

    NASA Astrophysics Data System (ADS)

    Illies, A.; Shevlin, P. B.; Childers, G.; Peschke, M.; Tsai, J.

    1995-08-01

    Mass spectrometry is routinely covered in undergraduate organic chemistry courses and a number of valuable laboratory experiments featuring its use have been discussed (1-7). Although such experiments work well at institutions with limited laboratory enrollments, we typically teach laboratories with enrollments of 160 or more in which it is difficult to allow each student to carry out a meaningful "hands on" mass spectrometry experiment. Since we feel that some practical experience with this technique is important, we have designed a simple gas chromatography-mass spectrometry (gc/ms) exercise that allows each student to analyze the products of a simple synthesis that they have performed. The exercise starts with the microscale SN2 synthesis of 1-bromobutane from 1-butanol as described by Williamson (8). The students complete the synthesis and place one drop of the distilled product in a screw capped vial. The vials are then sealed, labeled with the students name and taken to the mass spectrometry laboratory by a teaching assistant. Students are instructed to sign up for a 20-min block of time over the next few days in order to analyze their sample. When the student arrives at the laboratory, he or she adds 1 ml CH2Cl2 to the sample and injects 0.3 microliters of the solution into the gas chromatograph. The samples typically contain the 1-butanol starting material and the 1-bromobutane product along with traces of dibutyl ether. The figure shows a mass chromatogram along with the mass spectra of the starting material and product from an actual student run. For this analysis to be applicable to large numbers of students, the gc separation must be as rapid as possible. We have been able to analyze each sample in 6 minutes on a 30 m DB-5 capillary column with the following temperature program: 70 oC for 1 min, 70-80 oC at 10 oC/min, 86-140 oC at 67.5 oC/min, 140-210 oC at 70 oC/min, and 210 oC for 1 min. A mass range of 20-200 amu is scanned with a solvent delay of 2 min. Under these conditions each analysis takes the student about 10 min and two students are scheduled per 20 min block. Since the instrument is under computer control, students operate the computer during the run. As the peaks appear on the mass chromatogram, their mass spectra are obtained and the student decides which corresponds to product and evaluates product purity and the structure of impurities. There is ample time to display all spectra, conduct library searches, and print data. This relatively simple laboratory exercise has the advantage of allowing each student to carry out an analysis on his or her own product. The fact that a brominated product is obtained introduces a discussion of isotopic patterns in mass spectrometry. The experiment is scheduled to coincide with the lecture discussion of spectroscopic structure determination and after SN2 reactions have been covered. One of our mass spectrometer satellite data stations is interfaced with a "3-gun" projector in a large lecture hall allowing the display of actual mass spectra from our instrument to lecture sections. AcknowlegementThis work was partially supported by a grant, DUE9350846, from the National Science Foundation Division of Undergraduate Education Instrumentation and Laboratory Improvement Program. Literature Cited Brush, R. C.; Rice, G. W. J. Chem. Educ. 1994, 71, A293-A294. Asleson, G. L.; Doig, M. T.; Heldrich, F. J. J. Chem. Educ. 1993, 70, A290. Novak, M.; Heinrich, J. J. Chem. Educ. 1993, 70, A150. (b) Novak, M.; Heinrich, J.; Martin, K. A. J. Chem. Educ. 1993, 70, A103-104. Harman, C. S.; Myers, D. P.; Rittle, K. J. J. Chem. Educ. 1991, 68, 438-42. Mabbott, G. A. J. Chem. Educ. 1990, 67, 441-5. Hill, D. W.; McSharry, B. T.; Trzupek. J. Chem. Educ. 1988, 65, 907-10. Williamson, K. L. Macroscale and Microscale Organic Experiments, 2nd ed.; D. C. Heath: Lexington, MA, 1994; pp 247-51.

  8. Identification of subunit-subunit interaction sites in ?A-WT crystallin and mutant ?A-G98R crystallin using isotope-labeled cross-linker and mass spectrometry.

    PubMed

    Kannan, Rama; Santhoshkumar, Puttur; Mooney, Brian P; Sharma, K Krishna

    2013-01-01

    Cataract is characterized by progressive protein aggregation and loss of vision. ?-Crystallins are the major proteins in the lens responsible for maintaining transparency. They exist in the lens as highly polydisperse oligomers with variable numbers of subunits, and mutations in ?-crystallin are associated with some forms of cataract in humans. Because the stability of proteins is dependent on optimal subunit interactions, the structural transformations and aggregation of mutant proteins that underlie cataract formation can be understood best by identifying the residue-specific inter- and intra-subunit interactions. Chemical crosslinking combined with mass spectrometry is increasingly used to provide structural insights into intra- and inter-protein interactions. We used isotope-labeled cross-linker in combination with LC-MS/MS to determine the subunit-subunit interaction sites in cataract-causing mutant ?A-G98R crystallin. Peptides cross-linked by isotope-labeled (heavy and light forms) cross-linkers appear as doublets in mass spectra, thus facilitating the identification of cross-linker-containing peptides. In this study, we cross-linked wild-type (?A-WT) and mutant (?A-G98R) crystallins using the homobifunctional amine-reactive, isotope-labeled (d? and d?) cross-linker-BS²G (bis[sulfosuccinimidyl]glutarate). Tryptic in-solution digest of cross-linked complexes generates a wide array of peptide mixtures. Cross-linked peptides were enriched using strong cation exchange (SCX) chromatography followed by both MS and MS/MS to identify the cross-linked sites. We identified a distinct intermolecular interaction site between K88-K99 in the ?5 strand of the mutant ?A-G98R crystallin that is not found in wild-type ?A-crystallin. This interaction could explain the conformational instability and aggregation nature of the mutant protein that results from incorrect folding and assembly. PMID:23755258

  9. Methods for recalibration of mass spectrometry data

    DOEpatents

    Tolmachev, Aleksey V. (Richland, WA); Smith, Richard D. (Richland, WA)

    2009-03-03

    Disclosed are methods for recalibrating mass spectrometry data that provide improvement in both mass accuracy and precision by adjusting for experimental variance in parameters that have a substantial impact on mass measurement accuracy. Optimal coefficients are determined using correlated pairs of mass values compiled by matching sets of measured and putative mass values that minimize overall effective mass error and mass error spread. Coefficients are subsequently used to correct mass values for peaks detected in the measured dataset, providing recalibration thereof. Sub-ppm mass measurement accuracy has been demonstrated on a complex fungal proteome after recalibration, providing improved confidence for peptide identifications.

  10. Simultaneous quantification of phencynonate and its active metabolite N-demethyl phencynonate in human plasma using liquid chromatography and isotope-dilution mass spectrometry.

    PubMed

    Chen, Zhengang; Xie, Hui; Liu, Jinbo; Wang, Guangshun

    2015-09-01

    A sensitive and selective liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed to simultaneously quantify phencynonate (PCN) and its major metabolite N-demethyl phencynonate (DM-PCN) in human plasma. Following one-step liquid-liquid extraction, the analytes were separated on a reversed-phase C18 column. Methanol and 0.02% formic acid in 10 mM ammonium acetate (62:38, v/v) was used as isocratic mobile phase at a flow-rate of 0.3 mL/min. An API 5000 tandem mass spectrometer equipped with a Turbo IonSpray ionization source was used as the detector and was operated in the positive ion mode. Multiple reaction monitoring using the transition of m/z 358.4 ? m/z 156.2, m/z 344.4 ? m/z 142.2, and m/z 361.3 ? m/z 159.2 was performed to quantify PCN, DM-PCN, and the internal standard (D3 -PCN), respectively. This approach showed a lower limit of quantification of 10 pg/mL and 25 pg/mL for PCN and DM-PCN in plasma, respectively. This sensitivity was at least 50-fold superior to previously reported ones and thus enabled the approach well applicable to low-dose pharmacokinetic studies. The intra- and inter-day precisions were less than 14.2 % at each QC level for both PCN and DM-PCN. The inter-day relative errors ranged from -1.9% to -4.9% for PCN, and from 0.6% to 6.4% for DM-PCN. As a proof of principle, the validated method was successfully applied to simultaneous quantification of circulating PCN and DM-PCN in healthy subjects after a single oral administration of 2 mg phencynonate hydrochloride pellet. PMID:25994999

  11. Femtosecond filament-laser ablation molecular isotopic spectrometry

    NASA Astrophysics Data System (ADS)

    Hou, Huaming; Chan, George C.-Y.; Mao, Xianglei; Zheng, Ronger; Zorba, Vassilia; Russo, Richard E.

    2015-11-01

    A new remote sensing technology for real-time isotopic analysis is introduced: Femtosecond Filament-Induced Laser Ablation Molecular Isotopic Spectrometry (F2-LAMIS). The technique combines femtosecond (fs) laser filamentation and ablation-based molecular isotopic spectroscopy, thereby enabling isotopic analysis of samples at a distance, in ambient air and at ambient pressure conditions. Isotopic analysis of zirconium (Zr) samples by F2-LAMIS is demonstrated, and the molecular and atomic emission intensity, and properties of the filament-induced plasma generated at different filament propagation distances were investigated. Spectral fitting of F2-LAMIS spectra enabled semi-quantitative isotopic analysis without the use of calibration standards, which was independent of the filament propagation distance for the studied range. This technology provides new capabilities for direct isotopic ratio measurements at remote distances.

  12. Mass Spectrometry in the Home and Garden

    NASA Astrophysics Data System (ADS)

    Pulliam, Christopher J.; Bain, Ryan M.; Wiley, Joshua S.; Ouyang, Zheng; Cooks, R. Graham

    2015-02-01

    Identification of active components in a variety of chemical products used directly by consumers is described at both trace and bulk levels using mass spectrometry. The combination of external ambient ionization with a portable mass spectrometer capable of tandem mass spectrometry provides high chemical specificity and sensitivity as well as allowing on-site monitoring. These experiments were done using a custom-built portable ion trap mass spectrometer in combination with the ambient ionization methods of paper spray, leaf spray, and low temperature plasma ionization. Bactericides, garden chemicals, air fresheners, and other products were examined. Herbicide applied to suburban lawns was detected in situ on single leaves 5 d after application.

  13. Cortisol production rates measured by liquid chromatography/mass spectrometry

    SciTech Connect

    Esteban, N.V.; Yergey, A.L. )

    1990-04-01

    Cortisol production rates (FPRs) in physiologic and pathologic states in humans have been investigated over the past 30 years. However, there has been conflicting evidence concerning the validity of the currently accepted value of FPRs in humans (12 to 15 mg/m2/d) as determined by radiotracer methodology. The present study reviews previous methods proposed for the measurement of FPRs in humans and discusses the applications of the first method for the direct determination of 24-hour plasma FPRs during continuous administration of a stable isotope, using a thermospray high-pressure liquid chromatography-mass spectrometry technique. The technique is fast, sensitive, and, unlike gas chromatography-mass spectrometry methods, does not require derivatization, allowing on-line detection and quantification of plasma cortisol after a simple extraction procedure. The results of determination of plasma FPRs by stable tracer/mass spectrometry are directly in units of mass/time and, unlike radiotracer methods, are independent of any determination of volume of distribution or cortisol concentration. Our methodology offers distinct advantages over radiotracer techniques in simplicity and reliability since only single measurements of isotope ratios are required. The technique was validated in adrenalectomized patients. Circadian variations in daily FRPs were observed in normal volunteers, and, to date, results suggest a lower FRP in normal children and adults than previously believed. 88 references.

  14. Precise Measurement of Phenylalanine ?15N Values via Elemental Analysis-Isotope Ratio Mass Spectrometry Following Purification with High-Pressure Liquid Chromatography: A New Tool for Fine-Scale Paleo-Nitrogen Cycle Reconstructions

    NASA Astrophysics Data System (ADS)

    Broek, T.; Walker, B. D.; Batista, F. C.; Andreasen, D.; Hill, T. M.; Guilderson, T. P.; McCarthy, M.

    2012-12-01

    Compound specific isotope analysis of individual amino acids (CSI-AA) in organic paleoarchives is emerging as a powerful tool for reconstructing the paleo-nitrogen (N) cycle. Because the ?15N of phenylalanine (Phe) remains almost unchanged with diagenesis or trophic transfer it has been demonstrated to be the most promising AA proxy for the ?15N of primary production. However, the precise measurement of AA ?15N values is currently limited by the standard gas chromatography-isotope ratio mass spectrometer (GC-IRMS) approach. The key problem with this approach is that GC-IRMS ?15N precision (±1‰) is almost an order of magnitude lower than typical bulk ?15N measurements (±0.1‰), posing a significant problem for assessing fine scale changes within paleo-climate records. Additionally, required instrumentation is both expensive, and not widely available. Here we present an offline approach in which Phe is purified via high-pressure liquid chromatography (HPLC), using an analytical scale, mixed-phase column and automated fraction collection. ?13C and ?15N values of the fractions are then determined via standard elemental analysis-isotope ratio mass spectrometry (EA-IRMS). We evaluate the precision of this HPLC-EA-IRMS method vs. traditional GC-IRMS for Phe ?15N values of isotopic AA standards and various proteinaceous marine samples (marine coral, sediment, and cyanobacteria). Typical HPLC-EA-IRMS ?15N precision is ±0.1‰ for isotopic AA standards and ±0.5‰ for marine coral, sediment, and cyanobacteria samples compared to ±0.5‰ and ±1.0‰ for AA standards and samples analyzed by GC-IRMS. In order to demonstrate the viability of our approach, we present a comparison of a Phe ?15N record produced from a deep-sea bamboo coral specimen from Monterey Bay, CA, using our offline HPLC-EA-IRMS method vs. standard GC-IRMS. Each method produced equivalent Phe ?15N values within error, however, the HPLC-EA-IRMS method produced Phe ?15N values with over twice the precision of the traditional GC-IRMS method (HPLC-EA-IRMS standard deviation = 0.27‰ ± 0.14‰, GC-IRMS standard deviation = 0.60‰ ± 0.20‰). Our results suggest that this HPLC-EA-IRMS method represents a powerful, yet widely available tool for reconstructing fine scale N-cycling processes within paleoceanographic records.

  15. Performance evaluation of elemental analysis/isotope ratio mass spectrometry methods for the determination of the D/H ratio in tetramethylurea and other compounds--results of a laboratory inter-comparison.

    PubMed

    Bréas, Olivier; Thomas, Freddy; Zeleny, Reinhard; Calderone, Giovanni; Jamin, Eric; Guillou, Claude

    2007-01-01

    Tetramethylurea (TMU) with a certified D/H ratio is the internal standard for Site-specific Natural Isotope Fractionation measured by Nuclear Magnetic Resonance (SNIF-NMR) analysis of wine ethanol for detection of possible adulterations (Commission Regulation 2676/90). A new batch of a TMU certified reference material (CRM) is currently being prepared. Whereas SNIF-NMR has been employed up to now, Elemental Analysis/Isotope Ratio Mass Spectrometry ((2)H-EA-IRMS) was envisaged as the method of choice for value assignment of the new CRM, as more precise (better repeatable) data might be obtained, resulting in lower uncertainty of the certified value. In order to evaluate the accuracy and intra- and inter-laboratory reproducibility of (2)H-EA-IRMS methods, a laboratory inter-comparison was carried out by analysing TMU and other organic compounds, as well as some waters. The results revealed that experienced laboratories are capable of generating robust and well comparable data, which highlights the emerging potential of IRMS in food authenticity testing. However, a systematic bias between IRMS and SNIF-NMR reference data was observed for TMU; this lack of data consistency rules out the (2)H-IRMS technique for the characterisation measurement of the new TMU CRM. PMID:17428013

  16. Direct High-Precision Measurements of the (87)Sr/(86)Sr Isotope Ratio in Natural Water without Chemical Separation Using Thermal Ionization Mass Spectrometry Equipped with 10(12) ? Resistors.

    PubMed

    Li, Chao-Feng; Guo, Jing-Hui; Chu, Zhu-Yin; Feng, Lian-Jun; Wang, Xuan-Ce

    2015-07-21

    Thermal ionization mass spectrometry (TIMS) allows excellent precision for determining Sr isotope ratios in natural water samples. Traditionally, a chemical separation procedure using cation exchange resin has been employed to obtain a high purity Sr fraction from natural water, which makes sample preparation time-consuming. In this study, we present a rapid and precise method for the direct determination of the Sr isotope ratio of natural water using TIMS equipped with amplifiers with two 10(12) ? resistors. To eliminate the (87)Rb isobaric interference, Re ribbons are used as filaments, providing a significant advantage over W ribbons in the inhibition of Rb(+) emission, based on systematically examining a series of NIST SRM987 standard doping with various amounts of Rb using Re and W ribbons. To validate the applicability of our method, twenty-two natural water samples, including different water types (rain, snow, river, lake and drinking water), that show a large range in Sr content variations (2.54-922.8 ppb), were collected and analyzed from North and South China. Analytical results show good precision (0.003-0.005%, 2 RSE) and the method was further validated by comparative analysis of the same water with and without chemical separation. The method is simple and rapid, eliminates sample preparation time, and prevents potential contamination during complicated sample-preparation procedures. Therefore, a high sample throughput inherent to the TIMS can be fully utilized. PMID:26105121

  17. ?13C and ?18O isotopic composition of CaCO3 measured by continuous flow isotope ratio mass spectrometry: statistical evaluation and verification by application to Devils Hole core DH-11 calcite

    USGS Publications Warehouse

    Revesz, Kinga M.; Landwehr, Jurate M.

    2002-01-01

    A new method was developed to analyze the stable carbon and oxygen isotope ratios of small samples (400?±?20?µg) of calcium carbonate. This new method streamlines the classical phosphoric acid/calcium carbonate (H3PO4/CaCO3) reaction method by making use of a recently available Thermoquest-Finnigan GasBench II preparation device and a Delta Plus XL continuous flow isotope ratio mass spectrometer. Conditions for which the H3PO4/CaCO3 reaction produced reproducible and accurate results with minimal error had to be determined. When the acid/carbonate reaction temperature was kept at 26?°C and the reaction time was between 24 and 54?h, the precision of the carbon and oxygen isotope ratios for pooled samples from three reference standard materials was ?0.1 and ?0.2 per mill or ‰, respectively, although later analysis showed that materials from one specific standard required reaction time between 34 and 54?h for ?18O to achieve this level of precision. Aliquot screening methods were shown to further minimize the total error. The accuracy and precision of the new method were analyzed and confirmed by statistical analysis. The utility of the method was verified by analyzing calcite from Devils Hole, Nevada, for which isotope-ratio values had previously been obtained by the classical method. Devils Hole core DH-11 recently had been re-cut and re-sampled, and isotope-ratio values were obtained using the new method. The results were comparable with those obtained by the classical method with correlation?=?+0.96 for both isotope ratios. The consistency of the isotopic results is such that an alignment offset could be identified in the re-sampled core material, and two cutting errors that occurred during re-sampling then were confirmed independently. This result indicates that the new method is a viable alternative to the classical reaction method. In particular, the new method requires less sample material permitting finer resolution and allows automation of some processes resulting in considerable time savings. 

  18. Determination of Selected B-complex Vitamins in the NIST Multivitamin Reference Standard Material by Stable Isotope Dilution Mass Spectrometry (Experimental Biology, April, 2007, Washington, D.C.)

    Technology Transfer Automated Retrieval System (TEKTRAN)

    There is increased interest in accurately assessing the total dietary intake of vitamins from all sources, including foods and dietary supplements. Isotope dilution can be a definitive analytical method for very accurate concentration determinations. Thus, a liquid chromatographic (LC) isotope dilut...

  19. Electrospray Mass Spectrometry for Quantitative Plasma Proteome Analysis

    PubMed Central

    Wang, Hong; Hanash, Sam

    2015-01-01

    Summary Electrospray ionization mass spectrometry (ESI-MS) is an efficient soft ionization procedure for macro biomolecules. However, it is a rather delicate process to produce charged molecules for mass-to-charge ratio (m/z) based measurement. In this chapter, the mechanism of ESI is briefly presented, and the experimental pipeline for quantitative profiling of plasma proteins (prefractionation immunodepletion, protein isotope tagging, 2D-HPLC separation of intact proteins, and LC-MS) is presented as applied by our group in studies of cancer biomarker discovery. PMID:19544026

  20. Mass Spectrometry of Intact Membrane Protein Complexes

    PubMed Central

    Laganowsky, Arthur; Reading, Eamonn; Hopper, Jonathan T.S.; Robinson, Carol V.

    2014-01-01

    Mass spectrometry of intact soluble protein complexes has emerged as a powerful technique to study the stoichiometry, structure-function and dynamics of protein assemblies. Recent developments have extended this technique to the study of membrane protein complexes where it has already revealed subunit stoichiometries and specific phospholipid interactions. Here, we describe a protocol for mass spectrometry of membrane protein complexes. The protocol begins with preparation of the membrane protein complex enabling not only the direct assessment of stoichiometry, delipidation, and quality of the target complex, but also evaluation of the purification strategy. A detailed list of compatible non-ionic detergents is included, along with a protocol for screening detergents to find an optimal one for mass spectrometry, biochemical and structural studies. This protocol also covers the preparation of lipids for protein-lipid binding studies and includes detailed settings for a Q-ToF mass spectrometer after introduction of complexes from gold-coated nanoflow capillaries. PMID:23471109

  1. Application of real-time mass spectrometric techniques to environmental organic geochemistry. I. Computerized high resolution mass spectrometry and gas chromatography-low resolution mass spectrometry.

    PubMed

    Simoneit, B R; Smith, D H; Eglinton, G

    LOGOS (Smith et al. 1971), an integrated mass spectrometer/computer system, has been employed in a series of experiments which illustrate the utility of the automated techniques of real-time mass spectrometry in the study of organic compounds in the environment. These techniques are shown to be particularly useful in resolving complex mixtures of organic compounds encountered in environmental studies. Complete high resolution mass spectrometry, particularly when used in conjunction with combined gas chromatography/mass spectrometry, and auxiliary techniques such as stable isotopic labeling are described to illustrate the type and scope of information that may be obtained. Illustrative samples include extracts of air- and waterborne particulates, extracts of water-soluble organic material, and a DDT metabolite from sewage sludge. PMID:1235814

  2. STRUCTURAL CHARACTERIZATION OF REACTIVE DYES USING SECONDARY ION MASS SPECTROMETRY/TANDEM MASS SPECTROMETRY

    EPA Science Inventory

    Reactive Blue 19 (RB 19), its reactive form (RB 19-VS) and its hydrolyzed form, (RB 19-OH) were examined using liquid secondary ion mass spectrometry/tandem mass spectrometry (LSIMS/MS/MS) in the negative-ion mode under low-energy collision conditions (240-300 eV). tructurally ch...

  3. CHARACTERIZATION OF DOXYLAMINE AND PYRILAMINE METABOLITES VIA THERMOSPRAY/MASS SPECTROMETRY AND TANDEM MASS SPECTROMETRY

    EPA Science Inventory

    Analysis of doxylamine N-oxide and pyrilamine N-oxide as synthetic standards and biologically derived metabolites by thermospray mass spectrometry (TSP/MS) provided (M + H)+ ions for each metabolite. TSP/tandem mass spectrometry (TSP/MS/MS) of the (M + H)+ ions provided fragment ...

  4. Quantitative analysis of N-glycans from human alfa-acid-glycoprotein using stable isotope labeling and zwitterionic hydrophilic interaction capillary liquid chromatography electrospray mass spectrometry as tool for pancreatic disease diagnosis.

    PubMed

    Giménez, Estela; Balmaña, Meritxell; Figueras, Joan; Fort, Esther; de Bolós, Carme; Sanz-Nebot, Victòria; Peracaula, Rosa; Rizzi, Andreas

    2015-03-25

    In this work we demonstrate the potential of glycan reductive isotope labeling (GRIL) using [(12)C]- and [(13)C]-coded aniline and zwitterionic hydrophilic interaction capillary liquid chromatography electrospray mass spectrometry (?ZIC-HILIC-ESI-MS) for relative quantitation of glycosylation variants in selected glycoproteins present in samples from cancer patients. Human ?1-acid-glycoprotein (hAGP) is an acute phase serum glycoprotein whose glycosylation has been described to be altered in cancer and chronic inflammation. However, it is not clear yet whether some particular glycans in hAGP can be used as biomarker for differentiating between these two pathologies. In this work, hAGP was isolated by immunoaffinity chromatography (IAC) from serum samples of healthy individuals and from those suffering chronic pancreatitis and different stages of pancreatic cancer, respectively. After de-N-glycosylation, relative quantitation of the hAGP glycans was carried out using stable isotope labeling and ?ZIC-HILIC-ESI-MS analysis. First, protein denaturing conditions prior to PNGase F digestion were optimized to achieve quantitative digestion yields, and the reproducibility of the established methodology was evaluated with standard hAGP. Then, the proposed method was applied to the analysis of the clinical samples (control vs. pathological). Pancreatic cancer samples clearly showed an increase in the abundance of fucosylated glycans as the stage of the disease increases and this was unlike to samples from chronic pancreatitis. The results gained here indicate the mentioned glycan in hAGP as a candidate structure worth to be corroborated by an extended study including more clinical cases; especially those with chronic pancreatitis and initial stages of pancreatic cancer. Importantly, the results demonstrate that the presented methodology combining an enrichment of a target protein by IAC with isotope coded relative quantitation of N-glycans can be successfully used for targeted glycomics studies. The methodology is assumed being suitable as well for other such studies aimed at finding novel cancer associated glycoprotein biomarkers. PMID:25732693

  5. Comparative study of (13)C composition in ethanol and bulk dry wine using isotope ratio monitoring by mass spectrometry and by nuclear magnetic resonance as an indicator of vine water status.

    PubMed

    Guyon, Francois; van Leeuwen, Cornelis; Gaillard, Laetitia; Grand, Mathilde; Akoka, Serge; Remaud, Gérald S; Sabathié, Nathalie; Salagoïty, Marie-Hélène

    2015-12-01

    The potential of wine (13)C isotope composition (?(13)C) is presented to assess vine water status during grape ripening. Measurements of ?(13)C have been performed on a set of 32 authentic wines and their ethanol recovered after distillation. The data, obtained by isotope ratio monitoring by mass spectrometry coupled to an elemental analyser (irm-EA/MS), show a high correlation between ?(13)C of the bulk wine and its ethanol, indicating that the distillation step is not necessary when the wine has not been submitted to any oenological treatment. Therefore, the ethanol/wine ?(13)C correlation can be used as an indicator of possible enrichment of the grape must or the wine with exogenous organic compounds. Wine ethanol ?(13)C is correlated to predawn leaf water potential (R (2)?=?0.69), indicating that this parameter can be used as an indicator of vine water status. Position-specific (13)C analysis (PSIA) of ethanol extracted from wine, performed by isotope ratio monitoring by nuclear magnetic resonance (irm-(13)C NMR), confirmed the non-homogenous repartition of (13)C on ethanol skeleton. It is the ?(13)C of the methylene group of ethanol, compared to the methyl moiety, which is the most correlated to predawn leaf water potential, indicating that a phase of photorespiration of the vine during water stress period is most probably occurring due to stomata closure. However, position-specific (13)C analysis by irm-(13)C NMR does not offer a greater precision in the assessment of vine water status compared to direct measurement of ?(13)C on bulk wine by irm-EA/MS. PMID:26438472

  6. Attomole quantitation of protein separations with accelerator mass spectrometry

    SciTech Connect

    Vogel, J S; Grant, P G; Buccholz, B A; Dingley, K; Turteltaub, K W

    2000-12-15

    Quantification of specific proteins depends on separation by chromatography or electrophoresis followed by chemical detection schemes such as staining and fluorophore adhesion. Chemical exchange of short-lived isotopes, particularly sulfur, is also prevalent despite the inconveniences of counting radioactivity. Physical methods based on isotopic and elemental analyses offer highly sensitive protein quantitation that has linear response over wide dynamic ranges and is independent of protein conformation. Accelerator mass spectrometry quantifies long-lived isotopes such as 14C to sub-attomole sensitivity. We quantified protein interactions with small molecules such as toxins, vitamins, and natural biochemicals at precisions of 1-5% . Micro-proton-induced-xray-emission quantifies elemental abundances in separated metalloprotein samples to nanogram amounts and is capable of quantifying phosphorylated loci in gels. Accelerator-based quantitation is a possible tool for quantifying the genome translation into proteome.

  7. Capillary electrophoresis electrospray ionization mass spectrometry interface

    DOEpatents

    Smith, Richard D. (Richland, WA); Severs, Joanne C. (Hayward, CA)

    1999-01-01

    The present invention is an interface between a capillary electrophoresis separation capillary end and an electrospray ionization mass spectrometry emitter capillary end, for transporting an anolyte sample from a capillary electrophoresis separation capillary to a electrospray ionization mass spectrometry emitter capillary. The interface of the present invention has: (a) a charge transfer fitting enclosing both of the capillary electrophoresis capillary end and the electrospray ionization mass spectrometry emitter capillary end; (b) a reservoir containing an electrolyte surrounding the charge transfer fitting; and (c) an electrode immersed into the electrolyte, the electrode closing a capillary electrophoresis circuit and providing charge transfer across the charge transfer fitting while avoiding substantial bulk fluid transfer across the charge transfer fitting. Advantages of the present invention have been demonstrated as effective in providing high sensitivity and efficient analyses.

  8. Sequencing Cyclic Peptides by Multistage Mass Spectrometry

    PubMed Central

    Mohimani, Hosein; Yang, Yu-Liang; Liu, Wei-Ting; Hsieh, Pei-Wen; Dorrestein, Pieter C.; Pevzner, Pavel A.

    2012-01-01

    Some of the most effective antibiotics (e.g., Vancomycin and Daptomycin) are cyclic peptides produced by non-ribosomal biosynthetic pathways. While hundreds of biomedically important cyclic peptides have been sequenced, the computational techniques for sequencing cyclic peptides are still in their infancy. Previous methods for sequencing peptide antibiotics and other cyclic peptides are based on Nuclear Magnetic Resonance spectroscopy, and require large amount (miligrams) of purified materials that, for most compounds, are not possible to obtain. Recently, development of mass spectrometry based methods has provided some hope for accurate sequencing of cyclic peptides using picograms of materials. In this paper we develop a method for sequencing of cyclic peptides by multistage mass spectrometry, and show its advantages over single stage mass spectrometry. The method is tested on known and new cyclic peptides from Bacillus brevis, Dianthus superbus and Streptomyces griseus, as well as a new family of cyclic peptides produced by marine bacteria. PMID:21751357

  9. Analytical validation of accelerator mass spectrometry for pharmaceutical development

    PubMed Central

    Keck, Bradly D; Ognibene, Ted; Vogel, John S

    2011-01-01

    The validation parameters for pharmaceutical analyses were examined for the accelerator mass spectrometry measurement of 14C/C ratio, independent of chemical separation procedures. The isotope ratio measurement was specific (owing to the 14C label), stable across samples storage conditions for at least 1 year, linear over four orders of magnitude with an analytical range from 0.1 Modern to at least 2000 Modern (instrument specific). Furthermore, accuracy was excellent (between 1 and 3%), while precision expressed as coefficient of variation was between 1 and 6% determined primarily by radiocarbon content and the time spent analyzing a sample. Sensitivity, expressed as LOD and LLOQ was 1 and 10 attomoles of 14C, respectively (which can be expressed as compound equivalents) and for a typical small molecule labeled at 10% incorporated with 14C corresponds to 30 fg equivalents. Accelerator mass spectrometry provides a sensitive, accurate and precise method of measuring drug compounds in biological matrices. PMID:21083256

  10. Extracting cluster distributions from mass spectra: IsotopeFit

    PubMed Central

    Ralser, Stefan; Postler, Johannes; Harnisch, Martina; Ellis, Andrew M.; Scheier, Paul

    2015-01-01

    The availability of high resolution mass spectrometry in the study of atomic and molecular clusters opens up challenges for the interpretation of the data. In complex systems each resolved mass peak may contain contributions from multiple species because of the isotope structure of constituent elements and because a multitude of different types of clusters with different compositions are present. A computational procedure which can help to identify a specific cluster from this complex dataset and quantify its relative abundance would be extremely helpful to many who work in this field. Here some new software designed for this purpose, known as IsotopeFit, is described. PMID:26109907

  11. IDENTIFICATION OF TWO GLUCURONIDE METABOLITES OF DOXYLAMINE VIA THERMOSPRAY/MASS SPECTROMETRY AND THERMOSPRAY/MASS SPECTROMETRY/MASS SPECTROMETRY

    EPA Science Inventory

    Analysis of a high-pressure liquid chromatography fraction containing two urinary glucuronide metabolites of doxylamine by thermospray mass spectrometry (TSP/MS) provided (MH)+ ions for each metabolite. TSP/MS/MS of the (MH)+ ions provided a fragment ion characteristic of these m...

  12. Evaluation of the impact of matrix effect on quantification of pesticides in foods by gas chromatography-mass spectrometry using isotope-labeled internal standards.

    PubMed

    Yarita, Takashi; Aoyagi, Yoshie; Otake, Takamitsu

    2015-05-29

    The impact of the matrix effect in GC-MS quantification of pesticides in food using the corresponding isotope-labeled internal standards was evaluated. A spike-and-recovery study of nine target pesticides was first conducted using paste samples of corn, green soybean, carrot, and pumpkin. The observed analytical values using isotope-labeled internal standards were more accurate for most target pesticides than that obtained using the external calibration method, but were still biased from the spiked concentrations when a matrix-free calibration solution was used for calibration. The respective calibration curves for each target pesticide were also prepared using matrix-free calibration solutions and matrix-matched calibration solutions with blank soybean extract. The intensity ratio of the peaks of most target pesticides to that of the corresponding isotope-labeled internal standards was influenced by the presence of the matrix in the calibration solution; therefore, the observed slope varied. The ratio was also influenced by the type of injection method (splitless or on-column). These results indicated that matrix-matching of the calibration solution is required for very accurate quantification, even if isotope-labeled internal standards were used for calibration. PMID:25892640

  13. Nanostructure-initiator mass spectrometry biometrics

    DOEpatents

    Leclerc, Marion; Bowen, Benjamin; Northen, Trent

    2015-09-08

    Several embodiments described herein are drawn to methods of identifying an analyte on a subject's skin, methods of generating a fingerprint, methods of determining a physiological change in a subject, methods of diagnosing health status of a subject, and assay systems for detecting an analyte and generating a fingerprint, by nanostructure-initiator mass spectrometry (NIMS).

  14. Introduction to mass spectrometry-based proteomics.

    PubMed

    Matthiesen, Rune; Bunkenborg, Jakob

    2013-01-01

    Mass spectrometry has been widely applied to study biomolecules and one rapidly developing field is the global analysis of proteins, proteomics. Understanding and handling mass spectrometry data is a multifaceted task that requires many decisions to be made to get the most comprehensive information from an experiment. Later chapters in this book deal in-depth with various aspects of the process and how different tools can be applied to the many analytical challenges. This introductory chapter is intended as a basic introduction to mass spectrometry (MS)-based proteomics to set the scene for newcomers and give pointers to reference material. There are many applications of mass spectrometry in proteomics and each application is associated with some analytical choices, instrumental limitations and data processing steps that depend on the aim of the study and means of conducting it. Different aspects of the proteome can be explored by choosing the right combination of sample preparation, MS instrumentation and data processing. This chapter gives an outline for some of these commonly used setups and some of the key concepts, many of which are explored in greater depth in later chapters. PMID:23666720

  15. Pyrolysis Mass Spectrometry of Complex Organic Materials.

    ERIC Educational Resources Information Center

    Meuzelaar, Henk L. C.; And Others

    1984-01-01

    Illustrates the state of the art in pyrolysis mass spectrometry techniques through applications in: (1) structural determination and quality control of synthetic polymers; (2) quantitative analysis of polymer mixtures; (3) classification and structural characterization of fossil organic matter; and (4) nonsupervised numerical extraction of…

  16. Determination of 1-methyl-1H-1,2,4-triazole in soils contaminated by rocket fuel using solid-phase microextraction, isotope dilution and gas chromatography-mass spectrometry.

    PubMed

    Yegemova, Saltanat; Bakaikina, Nadezhda V; Kenessov, Bulat; Koziel, Jacek A; Nauryzbayev, Mikhail

    2015-10-01

    Environmental monitoring of Central Kazakhstan territories where heavy space booster rockets land requires fast, efficient, and inexpensive analytical methods. The goal of this study was to develop a method for quantitation of the most stable transformation product of rocket fuel, i.e., highly toxic unsymmetrical dimethylhydrazine - 1-methyl-1H-1,2,4-triazole (MTA) in soils using solid-phase microextraction (SPME) in combination with gas chromatography-mass spectrometry. Quantitation of organic compounds in soil samples by SPME is complicated by a matrix effect. Thus, an isotope dilution method was chosen using deuterated analyte (1-(trideuteromethyl)-1H-1,2,4-triazole; MTA-d3) for matrix effect control. The work included study of the matrix effect, optimization of a sample equilibration stage (time and temperature) after spiking MTA-d3 and validation of the developed method. Soils of different type and water content showed an order of magnitude difference in SPME effectiveness of the analyte. Isotope dilution minimized matrix effects. However, proper equilibration of MTA-d3 in soil was required. Complete MTA-d3 equilibration at temperatures below 40°C was not observed. Increase of temperature to 60°C and 80°C enhanced equilibration reaching theoretical MTA/MTA-d3 response ratios after 13 and 3h, respectively. Recoveries of MTA depended on concentrations of spiked MTA-d3 during method validation. Lowest spiked MTA-d3 concentration (0.24 mg kg(-1)) provided best MTA recoveries (91-121%). Addition of excess water to soil sample prior to SPME increased equilibration rate, but it also decreased method sensitivity. Method detection limit depended on soil type, water content, and was always below 1 mg kg(-1). The newly developed method is fully automated, and requires much lower time, labor and financial resources compared to known methods. PMID:26078153

  17. Precise measurement of Fe isotopes in marine samples by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS).

    PubMed

    de Jong, Jeroen; Schoemann, Véronique; Tison, Jean-Louis; Becquevort, Sylvie; Masson, Florence; Lannuzel, Delphine; Petit, Jérôme; Chou, Lei; Weis, Dominique; Mattielli, Nadine

    2007-04-18

    A novel analytical technique for isotopic analysis of dissolved and particulate iron (Fe) from various marine environments is presented in this paper. It combines coprecipitation of dissolved Fe (DFe) samples with Mg(OH)(2), and acid digestion of particulate Fe (PFe) samples with double pass chromatographic separation. Isotopic data were obtained using a Nu Plasma MC-ICP-MS in dry plasma mode, applying a combination of standard-sample bracketing and external normalization by Cu doping. Argon interferences were determined prior to each analysis and automatically subtracted during analysis. Sample size can be varied between 200 and 600 ng of Fe per measurement and total procedural blanks are better than 10 ng of Fe. Typical external precision of replicate analyses (1S.D.) is +/-0.07 per thousand on delta(56)Fe and +/-0.09 per thousand on delta(57)Fe while typical internal precision of a measurement (1S.E.) is +/-0.03 per thousand on delta(56)Fe and +/-0.04 per thousand on delta(57)Fe. Accuracy and precision were assured by the analysis of reference material IRMM-014, an in-house pure Fe standard, an in-house rock standard, as well as by inter-laboratory comparison using a hematite standard from ETH (Zürich). The lowest amount of Fe (200 ng) at which a reliable isotopic measurement could still be performed corresponds to a DFe or PFe concentration of approximately 2 nmol L(-1) for a 2 L sample size. To show the versatility of the method, results are presented from contrasting environments characterized by a wide range of Fe concentrations as well as varying salt content: the Scheldt estuary, the North Sea, and Antarctic pack ice. The range of DFe and PFe concentrations encountered in this investigation falls between 2 and 2000 nmol L(-1) Fe. The distinct isotopic compositions detected in these environments cover the whole range reported in previous studies of natural Fe isotopic fractionation in the marine environment, i.e. delta(56)Fe varies between -3.5 per thousand and +1.5 per thousand. The largest fractionations were observed in environments characterized by redox changes and/or strong Fe cycling. This demonstrates the potential use of Fe isotopes as a tool to trace marine biogeochemical processes involving Fe. PMID:17397660

  18. Fission Yield Measurements by Inductively Coupled Plasma Mass-Spectrometry

    SciTech Connect

    Irina Glagolenko; Bruce Hilton; Jeffrey Giglio; Daniel Cummings; Karl Grimm; Richard McKnight

    2009-11-01

    Correct prediction of the fission products inventory in irradiated nuclear fuels is essential for accurate estimation of fuel burnup, establishing proper requirements for spent fuel transportation and storage, materials accountability and nuclear forensics. Such prediction is impossible without accurate knowledge of neutron induced fission yields. Unfortunately, the accuracy of the fission yields reported in the ENDF/B-VII.0 library is not uniform across all of the data and much of the improvement is desired for certain isotopes and fission products. We discuss our measurements of cumulative fission yields in nuclear fuels irradiated in thermal and fast reactor spectra using Inductively Coupled Plasma Mass Spectrometry.

  19. Optimization Of A Mass Spectrometry Process

    SciTech Connect

    Lopes, Jose; Alegria, F. Correa; Redondo, Luis; Barradas, N. P.; Alves, E.; Rocha, Jorge

    2011-06-01

    In this paper we present and discuss a system developed in order to optimize the mass spectrometry process of an ion implanter. The system uses a PC to control and display the mass spectrum. The operator interacts with the I/O board, that interfaces with the computer and the ion implanter by a LabVIEW code. Experimental results are shown and the capabilities of the system are discussed.

  20. Preparation, certification and validation of a stable solid spike of uranium and plutonium coated with a cellulose derivative for the measurement of uranium and plutonium content in dissolved nuclear fuel by isotope dilution mass spectrometry.

    PubMed

    Surugaya, Naoki; Hiyama, Toshiaki; Verbruggen, André; Wellum, Roger

    2008-02-01

    A stable solid spike for the measurement of uranium and plutonium content in nitric acid solutions of spent nuclear fuel by isotope dilution mass spectrometry has been prepared at the European Commission Institute for Reference Materials and Measurements in Belgium. The spike contains about 50 mg of uranium with a 19.838% (235)U enrichment and 2 mg of plutonium with a 97.766% (239)Pu abundance in each individual ampoule. The dried materials were covered with a thin film of cellulose acetate butyrate as a protective organic stabilizer to resist shocks encountered during transportation and to eliminate flaking-off during long-term storage. It was found that the cellulose acetate butyrate has good characteristics, maintaining a thin film for a long time, but readily dissolving on heating with nitric acid solution. The solid spike containing cellulose acetate butyrate was certified as a reference material with certified quantities: (235)U and (239)Pu amounts and uranium and plutonium amount ratios, and was validated by analyzing spent fuel dissolver solutions of the Tokai reprocessing plant in Japan. This paper describes the preparation, certification and validation of the solid spike coated with a cellulose derivative. PMID:18270417

  1. Fast Atom Bombardment Mass Spectrometry.

    ERIC Educational Resources Information Center

    Rinehart, Kenneth L., Jr.

    1982-01-01

    Discusses reactions and characteristics of fast atom bombardment (FAB) mass spectroscopy in which samples are ionized in a condensed state by bombardment with xenon or argon atoms, yielding positive/negative secondary ions. Includes applications of FAB to structural problems and considers future developments using the technique. (Author/JN)

  2. Absorption mode FTICR mass spectrometry imaging.

    PubMed

    Smith, Donald F; Kilgour, David P A; Konijnenburg, Marco; O'Connor, Peter B; Heeren, Ron M A

    2013-12-01

    Fourier transform ion cyclotron resonance mass spectrometry offers the highest mass resolving power for molecular imaging experiments. This high mass resolving power ensures that closely spaced peaks at the same nominal mass are resolved for proper image generation. Typically higher magnetic fields are used to increase mass resolving power. However, a gain in mass resolving power can also be realized by phase correction of the data for absorption mode display. In addition to mass resolving power, absorption mode offers higher mass accuracy and signal-to-noise ratio over the conventional magnitude mode. Here, we present the first use of absorption mode for Fourier transform ion cyclotron resonance mass spectrometry imaging. The Autophaser algorithm is used to phase correct each spectrum (pixel) in the image, and then, these parameters are used by the Chameleon work-flow based data processing software to generate absorption mode "Datacubes" for image and spectral viewing. Absorption mode reveals new mass and spatial features that are not resolved in magnitude mode and results in improved selected ion image contrast. PMID:24175640

  3. Accelerator mass spectrometry for measurement of long-lived radioisotopes

    SciTech Connect

    Elmore, D.; Phillips, F.M.

    1987-05-01

    Particle accelerators, such as those built for research in nuclear physics, can also be used together with magnetic and electrostatic mass analyzers to measure rare isotopes at very low abundance ratios. All molecular ions can be eliminated when accelerated to energies of millions of electron volts. Some atomic isobars can be eliminated with the use of negative ions; others can be separated at high energies by measuring their rate of energy loss in a detector. The long-lived radioisotopes /sup 10/Be, /sup 14/C, /sup 26/Al, /sup 36/Cl, and /sup 129/I can now be measured in small natural samples having isotopic abundances in the range 10/sup -12/ to 10/sup -15/ and as few as 10/sup 5/ atoms. In the past few years, research applications of accelerator mass spectrometry have been concentrated in the earth sciences (climatology, cosmochemistry, environmental chemistry, geochronology, glaciology, hydrology, igneous petrogenesis, minerals exploration, sedimentology, and volcanology), in anthropology and archaeology (radiocarbon dating), and in physics (searches for exotic particles and measurement of half-lives). In addition, accelerator mass spectrometry may become an important tool for the materials and biological sciences. 98 references, 4 figures, 2 tables.

  4. Analysis of metal-EDTA complexes by electrospray mass spectrometry

    SciTech Connect

    Baron, D.; Hering, J.G.

    1998-07-01

    Solutions of the strong complexing agent ethylenediaminetetraacetic acid (EDTA) and Cu, Pb, Cd, Al, and Fe(III) were examined by electrospray mass spectrometry (ES/MS). Uncomplexed EDTA and metal-EDTA complexes survive the electrospray process intact and can be detected simultaneously by mass spectrometry. Best sensitivity was achieved in the positive ion mode in which EDTA and EDTA-metal complexes (present in solution as anions) were detected as protonated species with a single positive charge. Except for the protonation, the aqueous metal-EDTA complexes are preserved and neither fragmentation of complexes nor formation of clusters with more than one metal or ligand were observed in the mass spectra. Detection limits are between approximately 1 to 2 {micro}M for uncomplexed EDTA and for the Cu-EDTA and Pb-EDTA complexes, with a linear range up to 10{sup {minus}4} M. Calibrations based on solutions with equimolar concentrations of EDTA and Cu or Pb can be used to quantify EDTA-metal complexes in solutions with excess EDTA or metal, and in solutions with more than one metal present. Isotopic signatures of metals in the metal-ligand complexes are preserved, allowing the identification of the metal in a metal-ligand complex. Isotopic signatures of metals can therefore aid in the identification of metal-ligand complexes in unknown samples.

  5. Advanced Mass Spectrometers for Hydrogen Isotope Analyses

    SciTech Connect

    Chastagner, P.

    2001-08-01

    This report is a summary of the results of a joint Savannah River Laboratory (SRL) - Savannah River Plant (SRP) ''Hydrogen Isotope Mass Spectrometer Evaluation Program''. The program was undertaken to evaluate two prototype hydrogen isotope mass spectrometers and obtain sufficient data to permit SRP personnel to specify the mass spectrometers to replace obsolete instruments.

  6. Mercury determination in blood by gas chromatography-mass spectrometry.

    PubMed

    Aggarwal, S K; Kinter, M; Herold, D A

    1994-01-01

    A stable isotope dilution gas chromatography-mass spectrometry method using 196Hg as an internal standard is described for determining Hg in blood. In this method, the blood samples are not subjected to any digestion to avoid the loss of Hg. A solution of 0.6M HCl is used to free Hg present in blood from proteins. The pH of the solution is adjusted to 9 using borate buffer and Hg chelated using lithium bis(trifluoroethyl)dithiocarbamate. All isotope ratio measurements are made using an organic mass spectrometer. Overall precision values for the five major Hg isotopes relative to 202Hg are 1.6-2.3% when 10 ng samples of chelated Hg are analyzed. No appreciable memory or carryover effect is observed when two synthetic mixtures differing in 196Hg/202Hg ratios by a factor of 30 are sequentially analyzed. The method is validated by determining Hg in blood samples using isotope dilution GC-MS. PMID:7946912

  7. Secondary ion mass spectrometry (SIMS)! Seminar 4 (UN)!

    E-print Network

    ?umer, Slobodan

    ! ! Secondary ion mass spectrometry (SIMS)! Seminar 4 (UN)! ! ! ! ! ! ! ! ! Author: Nina Kovacic! ___________________________________________________________________________! ABSTRACT! ! Secondary ion mass spectrometry (SIMS) is an analytical experimental technique, used of primary ions, secondary particles are emitted. Few of them are charged ions (secondary ions), which

  8. Linking Mass Spectrometry with Toxicology for Emerging Water Contaminants

    EPA Science Inventory

    This overview presentation will discuss the benefits of combining mass spectrometry with toxicology. These benefits will be described for 3 main areas: (1) Toxicity assays used to test new environmental contaminants previously identified using mass spectrometry, such that furth...

  9. Trends in biochemical and biomedical applications of mass spectrometry

    NASA Astrophysics Data System (ADS)

    Gelpi, Emilio

    1992-09-01

    This review attempts an in-depth evaluation of progress and achievements made since the last 11th International Mass Spectrometry Conference in the application of mass spectrometric techniques to biochemistry and biomedicine. For this purpose, scientific contributions in this field at major international meetings have been monitored, together with an extensive appraisal of literature data covering the period from 1988 to 1991. A bibliometric evaluation of the MEDLINE database for this period provides a total of almost 4000 entries for mass spectrometry. This allows a detailed study of literature and geographical sources of the most frequent applications, of disciplines where mass spectrometry is most active and of types of sample and instrumentation most commonly used. In this regard major efforts according to number of publications (over 100 literature reports) are concentrated in countries like Canada, France, Germany, Italy, Japan, Sweden, UK and the USA. Also, most of the work using mass spectrometry in biochemistry and biomedicine is centred on studies on biotransformation, metabolism, pharmacology, pharmacokinetics and toxicology, which have been carried out on samples of blood, urine, plasma and tissue, by order of frequency of use. Human and animal studies appear to be evenly distributed in terms of the number of reports published in the literature in which the authors make use of experimental animals or describe work on human samples. Along these lines, special attention is given to the real usefulness of mass spectrometry (MS) technology in routine medical practice. Thus the review concentrates on evaluating the progress made in disease diagnosis and overall patient care. As regards prevailing techniques, GCMS continues to be the mainstay of the state of the art methods for multicomponent analysis, stable isotope tracer studies and metabolic profiling, while HPLC--MS and tandem MS are becoming increasingly important in biomedical research. However, despite the relatively large number of mass spectrometry reports in the biomedical sciences very few true routine applications are described, and recent technological innovations in instrumentation such as FABMS, electrospray, plasma or laser desorption have contributed relatively much more to structural biology, especially in biopolymer studies of macromolecules rather than to real life biomedical applications on patients and clinical problems.

  10. Advances in structure elucidation of small molecules using mass spectrometry

    PubMed Central

    Fiehn, Oliver

    2010-01-01

    The structural elucidation of small molecules using mass spectrometry plays an important role in modern life sciences and bioanalytical approaches. This review covers different soft and hard ionization techniques and figures of merit for modern mass spectrometers, such as mass resolving power, mass accuracy, isotopic abundance accuracy, accurate mass multiple-stage MS(n) capability, as well as hybrid mass spectrometric and orthogonal chromatographic approaches. The latter part discusses mass spectral data handling strategies, which includes background and noise subtraction, adduct formation and detection, charge state determination, accurate mass measurements, elemental composition determinations, and complex data-dependent setups with ion maps and ion trees. The importance of mass spectral library search algorithms for tandem mass spectra and multiple-stage MS(n) mass spectra as well as mass spectral tree libraries that combine multiple-stage mass spectra are outlined. The successive chapter discusses mass spectral fragmentation pathways, biotransformation reactions and drug metabolism studies, the mass spectral simulation and generation of in silico mass spectra, expert systems for mass spectral interpretation, and the use of computational chemistry to explain gas-phase phenomena. A single chapter discusses data handling for hyphenated approaches including mass spectral deconvolution for clean mass spectra, cheminformatics approaches and structure retention relationships, and retention index predictions for gas and liquid chromatography. The last section reviews the current state of electronic data sharing of mass spectra and discusses the importance of software development for the advancement of structure elucidation of small molecules. Electronic supplementary material The online version of this article (doi:10.1007/s12566-010-0015-9) contains supplementary material, which is available to authorized users. PMID:21289855

  11. Space Applications of Mass Spectrometry. Chapter 31

    NASA Technical Reports Server (NTRS)

    Hoffman, John H.; Griffin, Timothy P.; Limero, Thomas; Arkin, C. Richard

    2010-01-01

    Mass spectrometers have been involved in essentially all aspects of space exploration. This chapter outlines some of these many uses. Mass spectrometers have not only helped to expand our knowledge and understanding of the world and solar system around us, they have helped to put man safely in space and expand our frontier. Mass spectrometry continues to prove to be a very reliable, robust, and flexible analytical instrument, ensuring that its use will continue to help aid our investigation of the universe and this small planet that we call home.

  12. Mass Spectrometry Imaging under Ambient Conditions

    PubMed Central

    Wu, Chunping; Dill, Allison L.; Eberlin, Livia S.; Cooks, R. Graham; Ifa, Demian R.

    2012-01-01

    Mass spectrometry imaging (MSI) has emerged as an important tool in the last decade and it is beginning to show potential to provide new information in many fields owing to its unique ability to acquire molecularly specific images and to provide multiplexed information, without the need for labeling or staining. In MSI, the chemical identity of molecules present on a surface is investigated as a function of spatial distribution. In addition to now standard methods involving MSI in vacuum, recently developed ambient ionization techniques allow MSI to be performed under atmospheric pressure on untreated samples outside the mass spectrometer. Here we review recent developments and applications of MSI emphasizing the ambient ionization techniques of desorption electrospray ionization (DESI), laser ablation electrospray ionization (LAESI), probe electrospray ionization (PESI), desorption atmospheric pressure photoionization (DAPPI), femtosecond laser desorption ionization (fs-LDI), laser electrospray mass spectrometry (LEMS), infrared laser ablation metastable-induced chemical ionization (IR-LAMICI), liquid microjunction surface sampling probe mass spectrometry (LMJ-SSP MS), nanospray desorption electrospray ionization (nano-DESI), and plasma sources such as the low temperature plasma (LTP) probe and laser ablation coupled to flowing atmospheric-pressure afterglow (LA-FAPA). Included are discussions of some of the features of ambient MSI including the ability to implement chemical reactions with the goal of providing high abundance ions characteristic of specific compounds of interest and the use of tandem mass spectrometry to either map the distribution of targeted molecules with high specificity or to provide additional MS information in the structural identification of compounds. We also describe the role of bioinformatics in acquiring and interpreting the chemical and spatial information obtained through MSI, especially in biological applications for tissue diagnostic purposes. Finally, we discuss the challenges in ambient MSI and include perspectives on the future of the field. PMID:22996621

  13. Mass-dependent fractionation of nickel isotopes in meteoritic metal

    NASA Astrophysics Data System (ADS)

    Cook, David L.; Wadhwa, Meenakshi; Clayton, Robert N.; Dauphas, Nicolas; Janney, Philip E.; Davis, Andrew M.

    We measured nickel isotopes via multicollector inductively coupled plasma mass spectrometry (MC-ICPMS) in the bulk metal from 36 meteorites, including chondrites, pallasites, and irons (magmatic and non-magmatic). The Ni isotopes in these meteorites are mass fractionated; the fractionation spans an overall range of ?0.4‰ amu-1. The ranges of Ni isotopic compositions (relative to the SRM 986 Ni isotopic standard) in metal from iron meteorites (?0.0 to ?0.3‰ amu-1) and chondrites (?0.0 to ?0.2‰ amu-1) are similar, whereas the range in pallasite metal (?-0.1 to 0.0‰ amu-1) appears distinct. The fractionation of Ni isotopes within a suite of fourteen IIIAB irons (?0.0 to ?0.3‰ amu-1) spans the entire range measured in all magmatic irons. However, the degree of Ni isotopic fractionation in these samples does not correlate with their Ni content, suggesting that core crystallization did not fractionate Ni isotopes in a systematic way. We also measured the Ni and Fe isotopes in adjacent kamacite and taenite from the Toluca IAB iron meteorite. Nickel isotopes show clearly resolvable fractionation between these two phases; kamacite is heavier relative to taenite by ?0.4‰ amu-1. In contrast, the Fe isotopes do not show a resolvable fractionation between kamacite and taenite. The observed isotopic compositions of kamacite and taenite can be understood in terms of kinetic fractionation due to diffusion of Ni during cooling of the Fe-Ni alloy and the development of the Widmanstätten pattern.

  14. Impact of automation on mass spectrometry.

    PubMed

    Zhang, Yan Victoria; Rockwood, Alan

    2015-10-23

    Mass spectrometry coupled to liquid chromatography (LC-MS and LC-MS/MS) is an analytical technique that has rapidly grown in popularity in clinical practice. In contrast to traditional technology, mass spectrometry is superior in many respects including resolution, specificity, multiplex capability and has the ability to measure analytes in various matrices. Despite these advantages, LC-MS/MS remains high cost, labor intensive and has limited throughput. This specialized technology requires highly trained personnel and therefore has largely been limited to large institutions, academic organizations and reference laboratories. Advances in automation will be paramount to break through this bottleneck and increase its appeal for routine use. This article reviews these challenges, shares perspectives on essential features for LC-MS/MS total automation and proposes a step-wise and incremental approach to achieve total automation through reducing human intervention, increasing throughput and eventually integrating the LC-MS/MS system into the automated clinical laboratory operations. PMID:26341893

  15. A mass spectrometry proteomics data management platform.

    PubMed

    Sharma, Vagisha; Eng, Jimmy K; Maccoss, Michael J; Riffle, Michael

    2012-09-01

    Mass spectrometry-based proteomics is increasingly being used in biomedical research. These experiments typically generate a large volume of highly complex data, and the volume and complexity are only increasing with time. There exist many software pipelines for analyzing these data (each typically with its own file formats), and as technology improves, these file formats change and new formats are developed. Files produced from these myriad software programs may accumulate on hard disks or tape drives over time, with older files being rendered progressively more obsolete and unusable with each successive technical advancement and data format change. Although initiatives exist to standardize the file formats used in proteomics, they do not address the core failings of a file-based data management system: (1) files are typically poorly annotated experimentally, (2) files are "organically" distributed across laboratory file systems in an ad hoc manner, (3) files formats become obsolete, and (4) searching the data and comparing and contrasting results across separate experiments is very inefficient (if possible at all). Here we present a relational database architecture and accompanying web application dubbed Mass Spectrometry Data Platform that is designed to address the failings of the file-based mass spectrometry data management approach. The database is designed such that the output of disparate software pipelines may be imported into a core set of unified tables, with these core tables being extended to support data generated by specific pipelines. Because the data are unified, they may be queried, viewed, and compared across multiple experiments using a common web interface. Mass Spectrometry Data Platform is open source and freely available at http://code.google.com/p/msdapl/. PMID:22611296

  16. Monolithic multinozzle emitters for nanoelectrospray mass spectrometry

    DOEpatents

    Wang, Daojing (Daly City, CA); Yang, Peidong (Kensington, CA); Kim, Woong (Seoul, KR); Fan, Rong (Pasadena, CA)

    2011-09-20

    Novel and significantly simplified procedures for fabrication of fully integrated nanoelectrospray emitters have been described. For nanofabricated monolithic multinozzle emitters (NM.sup.2 emitters), a bottom up approach using silicon nanowires on a silicon sliver is used. For microfabricated monolithic multinozzle emitters (M.sup.3 emitters), a top down approach using MEMS techniques on silicon wafers is used. The emitters have performance comparable to that of commercially-available silica capillary emitters for nanoelectrospray mass spectrometry.

  17. [Sample preparation and bioanalysis in mass spectrometry].

    PubMed

    Bourgogne, Emmanuel; Wagner, Michel

    2015-01-01

    The quantitative analysis of compounds of clinical interest of low molecular weight (<1000 Da) in biological fluids is currently in most cases performed by liquid chromatography-mass spectrometry (LC-MS). Analysis of these compounds in biological fluids (plasma, urine, saliva, hair...) is a difficult task requiring a sample preparation. Sample preparation is a crucial part of chemical/biological analysis and in a sense is considered the bottleneck of the whole analytical process. The main objectives of sample preparation are the removal of potential interferences, analyte preconcentration, and converting (if needed) the analyte into a more suitable form for detection or separation. Without chromatographic separation, endogenous compounds, co-eluted products may affect a quantitative method in mass spectrometry performance. This work focuses on three distinct parts. First, quantitative bioanalysis will be defined, different matrices and sample preparation techniques currently used in bioanalysis by mass spectrometry of/for small molecules of clinical interest in biological fluids. In a second step the goals of sample preparation will be described. Finally, in a third step, sample preparation strategies will be made either directly ("dilute and shoot") or after precipitation. PMID:25582719

  18. Laser-Cooling-Assisted Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Schneider, Christian; Schowalter, Steven J.; Chen, Kuang; Sullivan, Scott T.; Hudson, Eric R.

    2014-09-01

    Mass spectrometry is used in a wide range of scientific disciplines including proteomics, pharmaceutics, forensics, and fundamental physics and chemistry. Given this ubiquity, there is a worldwide effort to improve the efficiency and resolution of mass spectrometers. However, the performance of all techniques is ultimately limited by the initial phase-space distribution of the molecules being analyzed. Here, we dramatically reduce the width of this initial phase-space distribution by sympathetically cooling the input molecules with laser-cooled, cotrapped atomic ions, improving both the mass resolution and detection efficiency of a time-of-flight mass spectrometer by over an order of magnitude. Detailed molecular-dynamics simulations verify the technique and aid with evaluating its effectiveness. This technique appears to be applicable to other types of mass spectrometers.

  19. Direct ionization methods in mass spectrometry: An overview.

    PubMed

    Klampfl, Christian W; Himmelsbach, Markus

    2015-08-26

    Within this paper a sub-group of ambient ionization mass spectrometry namely direct ionization mass spectrometry techniques are reviewed. They are characterized by the generation of an electrospray directly from the sample investigated. Prominent representatives include paper spray mass spectrometry, tissue spray mass spectrometry, probe electrospray ionization or thin-layer chromatography mass spectrometry. Applications of all major direct ionization techniques within different fields such as biomedical analysis, analysis of natural products, analysis of technical products and food analysis, just to name a few, are discussed and relevant parameters are listed in five Tables. PMID:26347167

  20. Guide to plutonium isotopic measurements using gamma-ray spectrometry

    SciTech Connect

    Lemming, J.F.; Rakel, D.A.

    1982-08-26

    Purpose of this guide is to assist those responsible for plutonium isotopic measurements in the application of gamma-ray spectrometry. Objectives are to promote an understanding of the measurement process, including its limitations and applicability, by reviewing the general features of a plutonium spectrum and identifying the quantities which must be extracted from the data; to introduce state-of-the-art analysis techniques by reviewing four isotopic analysis packages and identifying their differences; to establish the basis for measurement control and assurance by discussing means of authenticating the performance of a measurement system; and to prepare for some specific problems encountered in plutonium isotopic analyses by providing solutions from the practical experiences of several laboratories. 29 references, 12 figures, 17 tables.

  1. Electrospray Ionization Mass Spectrometry of hexanitrohexaazaisowurtzitane (CL-20)

    SciTech Connect

    Campbell, James A.; Szecsody, Jim E.; Devary, Brooks J.; Valenzuela, Blandina R.

    2007-09-03

    Hexanitrohexaazaisowurtzitane, (C6H6N12O12, MW 438) {CL-20}, is a high-energy propellent that has been recently developed and successfully tested (Nielsen et al. 1998). CL-20 releases more energy on ignition and is more stable to accidental detonation than currently used energetic materials. It is expected to replace many of the energetic materials currently being used by the Department of Defense (DoD). The EPA method 8330 (EPA 1997) for the analysis of explosives and metabolites in soils calls for the use of UV/Vis detection. High performance liquid chromatography has been used to quantify CL-20 and precursor concentration (Bazaki et al. 1998`) at relatively high concentrations. Fourier transform infrared (FTIR) spectroscopy has been used to identify different crystal forms of CL-20 (4 isomers; Kim et al. 1998). Campbell et al. (1997) utilized particle beam mass spectrometry for the analysis of enzymatic degradation of explosives. Introduction and recent improvements of ionization techniques such as electrospray (ES) have allowed the mass spectrometer to become more widely used in liquid chromatography. Schilling(1996) also examined explosive components and metabolites using electrospray (ES) and atmospheric pressure chemical ionization (APCI) liquid chromatography/mass spectrometry (LC/MS). Schilling’s results showed that compared to thermospray LC/MS, APCI and ES were more sensitive than thermospray by at least an order of magnitude. 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX), 10 nitroso-RDX metabolites, and other munitions in ground water have been analyzed using solid phase extraction and isotope dilution liquid chromatography-APCI mass spectrometry (Cassada et al. 1999). The method detection limits indicate that nitramine and nitroaromatic compounds can be routinely determined in ground water samples using electrospray LC/MS with concentration techniques utilizing solid-phase extraction. Miller et al. (1996) studied nitrated explosives with mobile phase additives to enhance the ESI intensities and spectral consistencies. Several of the explosives gave nitrate adduct ions in the negative mode with ammonium nitrate as the mobile phase. The nitramines RDX and 1,3,5,7-tetranitro-1,3,5,7 tetraazacyclooctane (HMX) showed the greatest enhancement in response of the explosives. Ammonium nitrate was used as the mobile phase and made it possible to obtain consistent and interpretable LC/MS spectra at the nanogram level. Campbell et al. (1999), Shi et al. (2000), and Goheen et al. (1999) utilized electrospray ionization mass spectrometry for the identification of degradation products of explosives. Yinon et al. (1997) used ESI and tandem mass spectrometry collision-induced dissociation to examine several nitramine compounds including trinitrotolutene (TNT), RDX, and pentaerythritol tetranitrate (PETN). The results indicate that explosives can be detected in the negative ion mode and characterized by various adduct ions. As an example, for nitroglycerin, the major adduct ion observed was (M+ONO2)-. In addition, Harvey et al. (1992) have used direct probe mass spectrometry for the analysis of degradation products of tetryl and its transformation products in soil. The negative ion electrospray mass spectrum of CL-20 is reported here. The major adduct ions observed under negative ion conditions were (M+Cl)- at m/z 473 and (M+ONO2) – at m/z 500. In addition, the results of mass spectrometry/mass spectrometry studies are also discussed.

  2. JOURNAL OF MASS SPECTROMETRY J. Mass Spectrom. 2008; 43: 10531062

    E-print Network

    Hammock, Bruce D.

    in the chlorine loss (in the ortho, meta, and para positions), the charge for the neutral radical (noncation-(2-chlorophenyl)propenoate by electron ionization mass spectrometry showed the distinct loss of an ortho chlorine exhibited loss of the distinctive chlorine from the 2-position of the phenyl ring. Analogous derivatives

  3. Highly sensitive isotope-dilution liquid-chromatography-electrospray ionization-tandem-mass spectrometry approach to study the drug-mediated modulation of dopamine and serotonin levels in Caenorhabditis elegans.

    PubMed

    Schumacher, Fabian; Chakraborty, Sudipta; Kleuser, Burkhard; Gulbins, Erich; Schwerdtle, Tanja; Aschner, Michael; Bornhorst, Julia

    2015-11-01

    Dopamine (DA) and serotonin (SRT) are monoamine neurotransmitters that play a key role in regulating the central and peripheral nervous system. Their impaired metabolism has been implicated in several neurological disorders, such as Parkinson's disease and depression. Consequently, it is imperative to monitor changes in levels of these low-abundant neurotransmitters and their role in mediating disease. For the first time, a rapid, specific and sensitive isotope-dilution liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed and validated for the quantification of DA and SRT in the nematode Caenorhabditis elegans (C. elegans). This model organism offers a unique approach for studying the effect of various drugs and environmental conditions on neurotransmitter levels, given by the conserved DA and SRT biology, including synaptic release, trafficking and formation. We introduce a novel sample preparation protocol incorporating the usage of sodium thiosulfate in perchloric acid as extraction medium that assures high recovery of the relatively unstable neurotransmitters monitored. Moreover, the use of both deuterated internal standards and the multiple reaction monitoring (MRM) technique allows for unequivocal quantification. Thereby, to the best of our knowledge, we achieve a detection sensitivity that clearly exceeds those of published DA and SRT quantification methods in various matrices. We are the first to show that exposure of C. elegans to the monoamine oxidase B (MAO-B) inhibitor selegiline or the catechol-O-methyltransferase (COMT) inhibitor tolcapone, in order to block DA and SRT degradation, resulted in accumulation of the respective neurotransmitter. Assessment of a behavioral output of the dopaminergic system (basal slowing response) corroborated the analytical LC-MS/MS data. Thus, utilization of the C. elegans model system in conjunction with our analytical method is well-suited to investigate drug-mediated modulation of the DA and SRT system in order to identify compounds with neuroprotective or regenerative properties. PMID:26452793

  4. Noninvasive measurement of smoking-associated N(3)-ethyladenine and N(7)-ethylguanine in human salivary DNA by stable isotope dilution nanoflow liquid chromatography-nanospray ionization tandem mass spectrometry.

    PubMed

    Chen, Hauh-Jyun Candy; Lin, Chao-Ray

    2014-02-10

    Evidence showed that ethylating agents are contained in cigarette smoke, which damage DNA producing ethylated DNA adducts, including N(3)-ethyladenine (3-EtAde) and N(7)-ethylguanine (7-EtGua). These two ethylpurines can be depurinated spontaneously and be repaired by enzymes and they have been detected in human urine. In this study, a highly specific and sensitive assay based on stable isotope dilution nanoflow liquid chromatography nanospray ionization tandem mass spectrometry (nanoLC-NSI/MS/MS) was used to measure 3-EtAde and 7-EtGua in human salivary DNA. These ethylpurines were released from DNA by neutral thermal hydrolysis and then enriched by a solid-phase extraction column before nanoLC-NSI/MS/MS analysis. The detection limits (S/N?3) of 3-EtA and 7-EtG were 15 fg (92 amol) and 10 fg (56 amol), respectively, injected on-column. The lower quantification limits of 3-EtAde and 7-EtGua were both 100 fg, i.e. 620 and 560 amol, respectively, corresponding to 9.4 and 8.6 adducts in 10(9) normal nucleotides, respectively, starting with as little as 20 ?g of DNA isolated from an average of 3 mL of saliva. The mean (±SD) levels of 3-EtAde in 15 smokers and 15 nonsmokers were 12.6±7.0 and 9.7±5.3 in 10(8) normal nucleotides, respectively, while those of 7-EtGua were 14.1±8.2 and 3.8±2.8 in 10(8) normal nucleotides in smokers and nonsmokers, respectively. Levels of 7-EtGua, but not 3-EtAde, were statistically significantly higher in smokers than in nonsmokers (p<0.0001). Furthermore, salivary 7-EtGua levels are significantly correlated with the number of cigarettes smoked per day as well as with the smoking index. This highly specific and sensitive stable isotope dilution nanoLC-NSI/MS/MS assay might be feasible in measuring 7-EtGua in human salivary DNA as a noninvasive biomarker for DNA damage induced by cigarette smoking. PMID:24300169

  5. Accelerator Mass Spectrometry of 129I towards its lower limits

    NASA Astrophysics Data System (ADS)

    Vockenhuber, Christof; Casacuberta, Nuria; Christl, Marcus; Synal, Hans-Arno

    2015-10-01

    We present the performance of Accelerator Mass Spectrometry (AMS) of 129I using the low energy facility TANDY of the Laboratory of Ion Beam Physics at ETH Zurich, Switzerland. Running the tandem accelerator at 300 kV in combination with helium as a stripper gas we obtain high transmission of >50% trough the accelerator for 129I ions in charge state 2+, molecules at mass 129 are sufficiently suppressed at appropriate stripper-gas pressures. While the high-energy spectrometer provides excellent suppression of the stable isotope 127I, mass-to-charge state (m/q) interferences are significantly reduced in 2+, allowing for measurements essentially free of background from other masses (isotopes and m/q interferences). The main challenge in the AMS of 129I comes from cross talk between samples in the ion source. With sufficient care low-level samples (129I/127I < 10-13) can be well measured, e.g. Woodward iodine was measured to 129I/127I = (3.4 ± 0.3) × 10-14, demonstrating that low-energy AMS of 129I provides both high overall efficiency and very low background.

  6. Laser Ablation Molecular Isotopic Spectrometry: Parameter influence on boron isotope measurements

    NASA Astrophysics Data System (ADS)

    Mao, Xianglei; Bol'shakov, Alexander A.; Perry, Dale L.; Sorkhabi, Osman; Russo, Richard E.

    2011-08-01

    Laser Ablation Molecular Isotopic Spectrometry (LAMIS) was recently reported for optical isotopic analysis of condensed samples in ambient air and at ambient pressure. LAMIS utilizes molecular emissions which exhibit larger isotopic spectral shits than in atomic transitions. For boron monoxide 10BO and 11BO, the isotopic shifts extend from 114 cm -1 (0.74 nm) to 145-238 cm -1 (5-8 nm) at the B2? + ( v = 0) ? X2? + ( v = 2) and A2? i ( v = 0) ? X2? + ( v = 3) transitions, respectively. These molecular isotopic shifts are over two orders of magnitude larger than the maximum isotopic shift of approximately 0.6 cm -1 in atomic boron. This paper describes how boron isotope abundance can be quantitatively determined using LAMIS and how atomic, ionic, and molecular optical emission develops in a plasma emanating from laser ablation of solid samples with various boron isotopic composition. We demonstrate that requirements for spectral resolution of the measurement system can be significantly relaxed when the isotopic abundance ratio is determined using chemometric analysis of spectra. Sensitivity can be improved by using a second slightly delayed laser pulse arriving into an expanding plume created by the first ablation pulse.

  7. 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 (?(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

  8. Uncoiling collagen: a multidimensional mass spectrometry study.

    PubMed

    Simon, H J; van Agthoven, M A; Lam, P Y; Floris, F; Chiron, L; Delsuc, M-A; Rolando, C; Barrow, M P; O'Connor, P B

    2016-01-01

    Mass spectrometry can be used to determine structural information about ions by activating precursors and analysing the resulting series of fragments. Two-dimensional Fourier transform ion cyclotron resonance mass spectrometry (2D FT-ICR MS) is a technique that correlates the mass-to-charge (m/z) ratio of fragment and precursor ions in a single spectrum. 2D FT-ICR MS records the fragmentation of all ions in a sample without the need for isolation. To analyse specific precursors, horizontal cross-sections of the spectrum (fragment ion scans) are taken, providing an alternative to conventional tandem mass spectrometry (MS/MS) experiments. In this work, 2D FT-ICR MS has been used to study the tryptic digest of type I collagen, a large protein. Fragment ion scans have been extracted from the 2D FT-ICR MS spectrum for precursor m/z ratios: 951.81, 850.41, 634.34, and 659.34, and 2D FT-ICR MS spectra are compared with a set of 1D MS/MS spectra using different fragmentation methods. The results show that two-dimensional mass spectrometry excells at MS/MS of complex mixtures, simplifying spectra by eliminating contaminant peaks, and aiding the identification of species in the sample. Currently, with desktop computers, 2D FT-ICR MS is limited by data processing power, a limitation which should be alleviated using cluster parallel computing. In order to explore 2D FT-ICR MS for collagen, with reasonable computing time, the resolution in the fragment ion dimension is limited to 256k data points (compared to 4M data points in 1D MS/MS spectra), but the vertical precursor ion dimension has 4096 lines, so the total data set is 1G data points (4 Gbytes). The fragment ion coverage obtained with a blind, unoptimized 2D FT-ICR MS experiment was lower than conventional MS/MS, but MS/MS information is obtained for all ions in the sample regardless of selection and isolation. Finally, although all 2D FT-ICR MS peak assignments were made with the aid of 1D FT-ICR MS data, these results demonstrate the promise of 2D FT-ICR MS as a technique for studying complex protein digest mixtures. PMID:26568361

  9. Mass spectrometry and inhomogeneous ion optics

    NASA Technical Reports Server (NTRS)

    White, F. A.

    1973-01-01

    Work done in several areas to advance the state of the art of magnetic mass spectrometers is described. The calculations and data necessary for the design of inhomogeneous field mass spectrometers, and the calculation of ion trajectories through such fields are presented. The development and testing of solid state ion detection devices providing the capability of counting single ions is discussed. New techniques in the preparation and operation of thermal-ionization ion sources are described. Data obtained on the concentrations of copper in rainfall and uranium in air samples using the improved thermal ionization techniques are presented. The design of a closed system static mass spectrometer for isotopic analyses is discussed. A summary of instrumental aspects of a four-stage mass spectrometer comprising two electrostatic and two 90 deg. magnetic lenses with a 122-cm radius used to study the interaction of ions with solids is presented.

  10. Indexing and Searching a Mass Spectrometry Database

    NASA Astrophysics Data System (ADS)

    Besenbacher, Søren; Schwikowski, Benno; Stoye, Jens

    Database preprocessing in order to create an index often permits considerable speedup in search compared to the iterated query of an unprocessed database. In this paper we apply index-based database lookup to a range search problem that arises in mass spectrometry-based proteomics: given a large collection of sparse integer sets and a sparse query set, find all the sets from the collection that have at least k integers in common with the query set. This problem arises when searching for a mass spectrum in a database of theoretical mass spectra using the shared peaks count as similarity measure. The algorithms can easily be modified to use the more advanced shared peaks intensity measure instead of the shared peaks count. We introduce three different algorithms solving these problems. We conclude by presenting some experiments using the algorithms on realistic data showing the advantages and disadvantages of the algorithms.

  11. Immunohistochemistry and mass spectrometry for highly multiplexed cellular molecular imaging.

    PubMed

    Levenson, Richard M; Borowsky, Alexander D; Angelo, Michael

    2015-04-01

    The role of immunohistochemistry (IHC) in the management of cancer has expanded to provide improved diagnostic classification, as well as guidance on disease prognosis, therapy, and relapse. These new tasks require evaluation of an increasing number of protein targets; however, conventional multiplexing, usually achieved using serial tissue sections stained for a single analyte per slide, can exhaust small biopsy specimens, complicate slide-to-slide protein expression correlation, and leave insufficient material for additional molecular assays. A new approach, mass spectrometry immunohistochemistry (MSIHC), compatible with high levels of target multiplexing and suitable for use on formalin-fixed, paraffin-embedded samples can circumvent many of these issues. The strategy employs antibodies that are labeled with elemental mass tags, such as isotopically pure lanthanides not typically found in biological specimens, rather than with typical fluorophores or chromogens. The metal-labeled antibodies are then detected in tissue using lasers or ion beams to liberate the tags for subsequent mass spectrometry detection. Within a given multiplexed IHC panel, the metal labels are selected so that their respective masses do not overlap. More than 30 antibodies have been imaged simultaneously, and up to 100 antibodies could potentially be detected at once if the full available mass spectrum is deployed. MSIHC has a number of advantages over conventional IHC techniques. Background due to autofluorescence is absent and the dynamic range is 10(5), exceeding immunofluorescence and chromogenic IHC by 100-fold and 1000-fold, respectively. Detection of labeled primary antibodies improves assay linearity over both chromogenic and fluorescent IHC. Multiplexed mass-tagged antibodies incubated simultaneously with tissue do not appear to cross-interfere, and because the mass tags do not degrade, samples are stable indefinitely. The imaging resolution of multiplexed ion-beam imaging can be better than light microscopy. With appropriate instrumentation, MSIHC has the potential to transform research and clinical pathology practice. PMID:25730370

  12. Study of CPP Mechanisms by Mass Spectrometry.

    PubMed

    Sagan, Sandrine; Bechara, Chérine; Burlina, Fabienne

    2015-01-01

    Studying the mechanisms of entry of cell-penetrating peptides (CPPs) requires reliable methods to measure their cellular uptake efficiency, monitor their metabolic stability, and identify their intracellular localization. We describe here a protocol based on the direct detection of peptides by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS), which allows the absolute quantification of the intact internalized species and the analysis of their intracellular degradation. This protocol can be easily applied to the simultaneous quantification of different species, for example mixtures of CPPs. PMID:26202265

  13. Recent advances in biomedical applications of accelerator mass spectrometry

    PubMed Central

    Hah, Sang Soo

    2009-01-01

    The use of radioisotopes has a long history in biomedical science, and the technique of accelerator mass spectrometry (AMS), an extremely sensitive nuclear physics technique for detection of very low-abundant, stable and long-lived isotopes, has now revolutionized high-sensitivity isotope detection in biomedical research, because it allows the direct determination of the amount of isotope in a sample rather than measuring its decay, and thus the quantitative analysis of the fate of the radiolabeled probes under the given conditions. Since AMS was first used in the early 90's for the analysis of biological samples containing enriched 14C for toxicology and cancer research, the biomedical applications of AMS to date range from in vitro to in vivo studies, including the studies of 1) toxicant and drug metabolism, 2) neuroscience, 3) pharmacokinetics, and 4) nutrition and metabolism of endogenous molecules such as vitamins. In addition, a new drug development concept that relies on the ultrasensitivity of AMS, known as human microdosing, is being used to obtain early human metabolism information of candidate drugs. These various aspects of AMS are reviewed and a perspective on future applications of AMS to biomedical research is provided. PMID:19534792

  14. Mass Spectrometry on Future Mars Landers

    NASA Technical Reports Server (NTRS)

    Brinckerhoff, W. B.; Mahaffy, P. R.

    2011-01-01

    Mass spectrometry investigations on the 2011 Mars Science Laboratory (MSL) and the 2018 ExoMars missions will address core science objectives related to the potential habitability of their landing site environments and more generally the near-surface organic inventory of Mars. The analysis of complex solid samples by mass spectrometry is a well-known approach that can provide a broad and sensitive survey of organic and inorganic compounds as well as supportive data for mineralogical analysis. The science value of such compositional information is maximized when one appreciates the particular opportunities and limitations of in situ analysis with resource-constrained instrumentation in the context of a complete science payload and applied to materials found in a particular environment. The Sample Analysis at Mars (SAM) investigation on MSL and the Mars Organic Molecule Analyzer (MOMA) investigation on ExoMars will thus benefit from and inform broad-based analog field site work linked to the Mars environments where such analysis will occur.

  15. Mass Spectrometry for Rapid Characterization of Microorganisms

    NASA Astrophysics Data System (ADS)

    Demirev, Plamen A.; Fenselau, Catherine

    2008-07-01

    Advances in instrumentation, proteomics, and bioinformatics have contributed to the successful applications of mass spectrometry (MS) for detection, identification, and classification of microorganisms. These MS applications are based on the detection of organism-specific biomarker molecules, which allow differentiation between organisms to be made. Intact proteins, their proteolytic peptides, and nonribosomal peptides have been successfully utilized as biomarkers. Sequence-specific fragments for biomarkers are generated by tandem MS of intact proteins or proteolytic peptides, obtained after, for instance, microwave-assisted acid hydrolysis. In combination with proteome database searching, individual biomarker proteins are unambiguously identified from their tandem mass spectra, and from there the source microorganism is also identified. Such top-down or bottom-up proteomics approaches permit rapid, sensitive, and confident characterization of individual microorganisms in mixtures and are reviewed here. Examples of MS-based functional assays for detection of targeted microorganisms, e.g., Bacillus anthracis, in environmental or clinically relevant backgrounds are also reviewed.

  16. FAPA mass spectrometry of designer drugs.

    PubMed

    Smoluch, Marek; Gierczyk, Blazej; Reszke, Edward; Babij, Michal; Gotszalk, Teodor; Schroeder, Grzegorz; Silberring, Jerzy

    2016-01-01

    Application of a flowing atmospheric-pressure afterglow ion source for mass spectrometry (FAPA-MS) for the analysis of designer drugs is described. In this paper, we present application of FAPA MS for identification of exemplary psychotropic drugs: JWH-122, 4BMC, Pentedrone, 3,4-DNNC and ETH-CAT. We have utilized two approaches for introducing samples into the plasma stream; first in the form of a methanolic aerosol from the nebulizer, and the second based on a release of vapors from the electrically heated crucible by thermal desorption. The analytes were ionized by FAPA and identified in the mass analyzer. The order of release of the compounds depends on their volatility. These methods offer fast and reliable structural information, without pre-separation, and can be an alternative to the Electron Impact, GC/MS, and ESI for fast analysis of designer-, and other psychoactive drugs. PMID:26695230

  17. Protein Sequencing with Tandem Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Ziady, Assem G.; Kinter, Michael

    The recent introduction of electrospray ionization techniques that are suitable for peptides and whole proteins has allowed for the design of mass spectrometric protocols that provide accurate sequence information for proteins. The advantages gained by these approaches over traditional Edman Degradation sequencing include faster analysis and femtomole, sometimes attomole, sensitivity. The ability to efficiently identify proteins has allowed investigators to conduct studies on their differential expression or modification in response to various treatments or disease states. In this chapter, we discuss the use of electrospray tandem mass spectrometry, a technique whereby protein-derived peptides are subjected to fragmentation in the gas phase, revealing sequence information for the protein. This powerful technique has been instrumental for the study of proteins and markers associated with various disorders, including heart disease, cancer, and cystic fibrosis. We use the study of protein expression in cystic fibrosis as an example.

  18. Radiocarbon positive-ion mass spectrometry

    NASA Astrophysics Data System (ADS)

    Freeman, Stewart P. H. T.; Shanks, Richard P.; Donzel, Xavier; Gaubert, Gabriel

    2015-10-01

    Proof-of-principle of a new mass spectrometric technique for radiocarbon measurement is demonstrated. Interfering nitrogen and hydrocarbon molecules are largely eliminated in a charge-exchange cell operating on non-metallic gas. The positive-to-negative ion conversion is the reverse of that conventionally used in accelerator mass spectrometry (AMS) and is compatible with plasma ion sources that may be significantly more efficient and capable of greater output than are AMS sputter ion sources. The Nanogan electron cyclotron resonance (ECR) ion source employed exhibited no sample memory and the >50 kyrs age range of AMS was reproduced. A bespoke prototype new instrument is now required to optimise the plasma and cell physics and to realise hypothetical performance gains over AMS.

  19. Determination of hexabromocyclododecane by flowing atmospheric pressure afterglow mass spectrometry.

    PubMed

    Smoluch, Marek; Silberring, Jerzy; Reszke, Edward; Kuc, Joanna; Grochowalski, Adam

    2014-10-01

    The first application of a flowing atmospheric-pressure afterglow ion source for mass spectrometry (FAPA-MS) for the chemical characterization and determination of hexabromocyclododecane (HBCD) is presented. The samples of technical HBCD and expanded polystyrene foam (EPS) containing HBCD as a flame retardant were prepared by dissolving the appropriate solids in dichloromethane. The ionization of HBCD was achieved with a prototype FAPA source. The ions were detected in the negative-ion mode. The ions corresponding to a deprotonated HBCD species (m/z 640.7) as well as chlorine (m/z 676.8), nitrite (m/z 687.8) and nitric (m/z 703.8) adducts were observed in the spectra. The observed isotope pattern is characteristic for a compound containing six bromine atoms. This technique is an effective approach to detect HBCD, which is efficiently ionized in a liquid phase, resulting in high detection efficiency and sensitivity. PMID:25059130

  20. Mass Spectrometry-Based Label-Free Quantitative Proteomics

    PubMed Central

    Zhu, Wenhong; Smith, Jeffrey W.; Huang, Chun-Ming

    2010-01-01

    In order to study the differential protein expression in complex biological samples, strategies for rapid, highly reproducible and accurate quantification are necessary. Isotope labeling and fluorescent labeling techniques have been widely used in quantitative proteomics research. However, researchers are increasingly turning to label-free shotgun proteomics techniques for faster, cleaner, and simpler results. Mass spectrometry-based label-free quantitative proteomics falls into two general categories. In the first are the measurements of changes in chromatographic ion intensity such as peptide peak areas or peak heights. The second is based on the spectral counting of identified proteins. In this paper, we will discuss the technologies of these label-free quantitative methods, statistics, available computational software, and their applications in complex proteomics studies. PMID:19911078

  1. High-Speed Mass Spectrometry Hadamard Transform Time-of-Flight Mass

    E-print Network

    Zare, Richard N.

    High-Speed Mass Spectrometry Hadamard Transform Time-of-Flight Mass Spectrometry: More Signal, More method is time-of-flight (TOF) mass spectrometry (MS), in which ions of different masses are given acceleration, the flight time of the ion is measured over a fixed distance between a starting point and the ion

  2. Crux: rapid open source protein tandem mass spectrometry analysis.

    PubMed

    McIlwain, Sean; Tamura, Kaipo; Kertesz-Farkas, Attila; Grant, Charles E; Diament, Benjamin; Frewen, Barbara; Howbert, J Jeffry; Hoopmann, Michael R; Käll, Lukas; Eng, Jimmy K; MacCoss, Michael J; Noble, William Stafford

    2014-10-01

    Efficiently and accurately analyzing big protein tandem mass spectrometry data sets requires robust software that incorporates state-of-the-art computational, machine learning, and statistical methods. The Crux mass spectrometry analysis software toolkit ( http://cruxtoolkit.sourceforge.net ) is an open source project that aims to provide users with a cross-platform suite of analysis tools for interpreting protein mass spectrometry data. PMID:25182276

  3. Crux: Rapid Open Source Protein Tandem Mass Spectrometry Analysis

    PubMed Central

    2015-01-01

    Efficiently and accurately analyzing big protein tandem mass spectrometry data sets requires robust software that incorporates state-of-the-art computational, machine learning, and statistical methods. The Crux mass spectrometry analysis software toolkit (http://cruxtoolkit.sourceforge.net) is an open source project that aims to provide users with a cross-platform suite of analysis tools for interpreting protein mass spectrometry data. PMID:25182276

  4. Toward single-molecule nanomechanical mass spectrometry

    PubMed Central

    Naik, A. K.; Hanay, M. S.; Hiebert, W. K.; Feng, X. L.; Roukes, M. L.

    2009-01-01

    Mass spectrometry (MS) provides rapid and quantitative identification of protein species with relatively low sample consumption. Yet with the trend toward biological analysis at increasingly smaller scales, ultimately down to the volume of an individual cell, MS with few-to-single molecule sensitivity will be required. Nanoelectromechanical systems (NEMS) provide unparalleled mass sensitivity, which is now sufficient for the detection of individual molecular species in real time. Here we report the first demonstration of MS based on single-biological-molecule detection with NEMS. In our NEMS-MS system, nanoparticles and protein species are introduced by electrospray injection from fluid phase in ambient conditions into vacuum and subsequently delivered to the NEMS detector by hexapole ion optics. Precipitous frequency shifts, proportional to the mass, are recorded in real time as analytes adsorb, one-by-one, onto a phase-locked, ultrahigh frequency NEMS resonator. These first NEMS-MS spectra, obtained with modest mass sensitivity from only several hundred mass adsorption events, presage the future capabilities of this approach. We also outline the substantial improvements that are feasible in the near term, some of which are unique to NEMS-MS. PMID:19581898

  5. Comprehensive profiling of mercapturic acid metabolites from dietary acrylamide as short-term exposure biomarkers for evaluation of toxicokinetics in rats and daily internal exposure in humans using isotope dilution ultra-high performance liquid chromatography tandem mass spectrometry.

    PubMed

    Zhang, Yu; Wang, Qiao; Cheng, Jun; Zhang, Jingshun; Xu, Jiaojiao; Ren, Yiping

    2015-09-24

    Mercapturic acid metabolites from dietary acrylamide are important short-term exposure biomarkers for evaluating the in vivo toxicity of acrylamide. Most of studies have focused on the measurement of two metabolites, N-acetyl-S-(2-carbamoylethyl)-l-cysteine (AAMA) and N-acetyl-S-(2-carbamoyl-2-hydroxyethyl)-l-cysteine (GAMA). Thus, the comprehensive profile of acrylamide urinary metabolites cannot be fully understood. We developed an isotope dilution ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) method for the simultaneous determination of all four mercapturic acid adducts of acrylamide and its primary metabolite glycidamide under the electroscopy ionization negative (ESI-) mode in the present study. The limit of detection (LOD) and limit of quantification (LOQ) of the analytes ranged 0.1-0.3 ng/mL and 0.4-1.0 ng/mL, respectively. The recovery rates with low, intermediate and high spiking levels were calculated as 95.5%-105.4%, 98.2%-114.0% and 92.2%-108.9%, respectively. Acceptable within-laboratory reproducibility (RSD<7.0%) substantially supported the use of current method for robust analysis. Rapid pretreatment procedures and short run time (8 min per sample) ensured good efficiency of metabolism profiling, indicating a wide application for investigating short-term internal exposure of dietary acrylamide. Our proposed UHPLC-MS/MS method was successfully applied to the toxicokinetic study of acrylamide in rats. Meanwhile, results of human urine analysis indicated that the levels of N-acetyl-S-(2-carbamoylethyl)-l-cysteine-sulfoxide (AAMA-sul), which did not appear in the mercapturic acid metabolites in rodents, were more than the sum of GAMA and N-acetyl-S-(1-carbamoyl-2-hydroxyethyl)-l-cysteine (iso-GAMA). Thus, AAMA-sul may alternatively become a specific biomarker for investigating the acrylamide exposure in humans. Current proposed method provides a substantial methodology support for comprehensive profiling of toxicokinetics and daily internal exposure evaluations of acrylamide in vivo. PMID:26423628

  6. Raman spectroscopic and mass spectrometric investigations of the hydrogen isotopes and isotopically labelled methane

    SciTech Connect

    Jewett, J.R., Fluor Daniel Hanford

    1997-02-24

    Suitable analytical methods must be tested and developed for monitoring the individual process steps within the fuel cycle of a fusion reactor and for tritium accountability. The utility of laser-Raman spectroscopy accompanied by mass spectrometry with an Omegatron was investigated using the analysis of all hydrogen isotopes and isotopically labeled methanes as an example. The Omegatron is useful for analyzing all hydrogen isotopes mixed with the stable helium isotopes. The application of this mass spectrometer were demonstrated by analyzing mixtures of deuterated methanes. In addition, it was employed to study the radiochemical Witzbach exchange reaction between tritium and methanes. A laser-Raman spectrometer was designed for analysis of tritium-containing gases and was built from individual components. A tritium-compatible, metal-sealed Raman cuvette having windows with good optical properties and additional means for measuring the stray light was first used successfully in this work. The Raman spectra of the hydrogen isotopes were acquired in the pure rotation mode and in the rotation-vibration mode and were used for on. The deuterated methanes were measured by Raman spectroscopy, the wavenumbers determined were assigned to the corresponding vibrations, and the wavenumbers for the rotational fine-structure were summarized in tables. The fundamental Vibrations of the deuterated methanes produced Witzbach reactions were detected and assigned. The fundamental vibrations of the molecules were obtained with Raman spectroscopy for the first time in this work. The @-Raman spectrometer assembled is well suited for the analysis of tritium- containing gases and is practical in combination with mass spectrometry using an Omegatron, for studying gases used in fusion.

  7. Multinozzle Emitter Arrays for Nanoelectrospray Mass Spectrometry

    SciTech Connect

    Mao, Pan; Wang, Hung-Ta; Yang, Peidong; Wang, Daojing

    2011-06-16

    Mass spectrometry (MS) is the enabling technology for proteomics and metabolomics. However, dramatic improvements in both sensitivity and throughput are still required to achieve routine MS-based single cell proteomics and metabolomics. Here, we report the silicon-based monolithic multinozzle emitter array (MEA), and demonstrate its proof-of-principle applications in high-sensitivity and high-throughput nanoelectrospray mass spectrometry. Our MEA consists of 96 identical 10-nozzle emitters in a circular array on a 3-inch silicon chip. The geometry and configuration of the emitters, the dimension and number of the nozzles, and the micropillar arrays embedded in the main channel, can be systematically and precisely controlled during the microfabrication process. Combining electrostatic simulation and experimental testing, we demonstrated that sharpened-end geometry at the stem of the individual multinozzle emitter significantly enhanced the electric fields at its protruding nozzle tips, enabling sequential nanoelectrospray for the high-density emitter array. We showed that electrospray current of the multinozzle emitter at a given total flow rate was approximately proportional to the square root of the number of its spraying-nozzles, suggesting the capability of high MS sensitivity for multinozzle emitters. Using a conventional Z-spray mass spectrometer, we demonstrated reproducible MS detection of peptides and proteins for serial MEA emitters, achieving sensitivity and stability comparable to the commercial capillary emitters. Our robust silicon-based MEA chip opens up the possibility of a fully-integrated microfluidic system for ultrahigh-sensitivity and ultrahigh-throughput proteomics and metabolomics.

  8. Multinozzle Emitter Arrays for Nanoelectrospray Mass Spectrometry

    PubMed Central

    Mao, Pan; Wang, Hung-Ta; Yang, Peidong; Wang, Daojing

    2011-01-01

    Mass spectrometry (MS) is the enabling technology for proteomics and metabolomics. However, dramatic improvements in both sensitivity and throughput are still required to achieve routine MS-based single cell proteomics and metabolomics. Here, we report the silicon-based monolithic multinozzle emitter array (MEA), and demonstrate its proof-of-principle applications in high-sensitivity and high-throughput nanoelectrospray mass spectrometry. Our MEA consists of 96 identical 10-nozzle emitters in a circular array on a 3-inch silicon chip. The geometry and configuration of the emitters, the dimension and number of the nozzles, and the micropillar arrays embedded in the main channel, can be systematically and precisely controlled during the microfabrication process. Combining electrostatic simulation and experimental testing, we demonstrated that sharpened-end geometry at the stem of the individual multinozzle emitter significantly enhanced the electric fields at its protruding nozzle tips, enabling sequential nanoelectrospray for the high-density emitter array. We showed that electrospray current of the multinozzle emitter at a given total flow rate was approximately proportional to the square root of the number of its spraying-nozzles, suggesting the capability of high MS sensitivity for multinozzle emitters. Using a conventional Z-spray mass spectrometer, we demonstrated reproducible MS detection of peptides and proteins for serial MEA emitters, achieving sensitivity and stability comparable to the commercial capillary emitters. Our robust silicon-based MEA chip opens up the possibility of a fully-integrated microfluidic system for ultrahigh-sensitivity and ultrahigh-throughput proteomics and metabolomics. PMID:21728281

  9. Laser Mass Spectrometry in Planetary Science

    SciTech Connect

    Wurz, P.; Whitby, J. A.; Managadze, G. G.

    2009-06-16

    Knowing the chemical, elemental, and isotopic composition of planetary objects allows the study of their origin and evolution within the context of our solar system. Exploration plans in planetary research of several space agencies consider landing spacecraft for future missions. Although there have been successful landers in the past, more landers are foreseen for Mars and its moons, Venus, the jovian moons, and asteroids. Furthermore, a mass spectrometer on a landed spacecraft can assist in the sample selection in a sample-return mission and provide mineralogical context, or identify possible toxic soils on Mars for manned Mars exploration. Given the resources available on landed spacecraft mass spectrometers, as well as any other instrument, have to be highly miniaturised.

  10. Neutral particle mass spectrometry with nanomechanical systems.

    PubMed

    Sage, Eric; Brenac, Ariel; Alava, Thomas; Morel, Robert; Dupré, Cécilia; Hanay, Mehmet Selim; Roukes, Michael L; Duraffourg, Laurent; Masselon, Christophe; Hentz, Sébastien

    2015-01-01

    Current approaches to mass spectrometry (MS) require ionization of the analytes of interest. For high-mass species, the resulting charge state distribution can be complex and difficult to interpret correctly. Here, using a setup comprising both conventional time-of-flight MS (TOF-MS) and nano-electromechanical systems-based MS (NEMS-MS) in situ, we show directly that NEMS-MS analysis is insensitive to charge state: the spectrum consists of a single peak whatever the species' charge state, making it significantly clearer than existing MS analysis. In subsequent tests, all the charged particles are electrostatically removed from the beam, and unlike TOF-MS, NEMS-MS can still measure masses. This demonstrates the possibility to measure mass spectra for neutral particles. Thus, it is possible to envisage MS-based studies of analytes that are incompatible with current ionization techniques and the way is now open for the development of cutting-edge system architectures with unique analytical capability. PMID:25753929

  11. Detection of Gunshot Residues Using Mass Spectrometry

    PubMed Central

    Blanes, Lucas; Cole, Nerida; Doble, Philip; Roux, Claude

    2014-01-01

    In recent years, forensic scientists have become increasingly interested in the detection and interpretation of organic gunshot residues (OGSR) due to the increasing use of lead- and heavy metal-free ammunition. This has also been prompted by the identification of gunshot residue- (GSR-) like particles in environmental and occupational samples. Various techniques have been investigated for their ability to detect OGSR. Mass spectrometry (MS) coupled to a chromatographic system is a powerful tool due to its high selectivity and sensitivity. Further, modern MS instruments can detect and identify a number of explosives and additives which may require different ionization techniques. Finally, MS has been applied to the analysis of both OGSR and inorganic gunshot residue (IGSR), although the “gold standard” for analysis is scanning electron microscopy with energy dispersive X-ray microscopy (SEM-EDX). This review presents an overview of the technical attributes of currently available MS and ionization techniques and their reported applications to GSR analysis. PMID:24977168

  12. China's food safety regulation and mass spectrometry.

    PubMed

    Chu, Xiaogang; Zhang, Feng; Nie, Xuemei; Wang, Wenzhi; Feng, Feng

    2011-01-01

    Food safety is essential to people's health and people's livelihood. To ensure that food safety is an important current strategy of the governments, both regulation and standardization are important support for implementing this strategic initiative effectively. The status and prospects of China's food laws, regulations, and standards system are introduced. China now has established a complete law regime providing a sound foundation and good environment for keeping the health of people, maintaining the order of social economy and promoting the international trade of food. At the same time, it is undoubtedly important to strengthen standardization and improve the food safety standards system. In the administration of food safety, mass spectrometry is becoming more and more important and many analytical methods developed in China are based on its application. PMID:21643903

  13. Mass Spectrometry Methodology in Lipid Analysis

    PubMed Central

    Li, Lin; Han, Juanjuan; Wang, Zhenpeng; Liu, Jian’an; Wei, Jinchao; Xiong, Shaoxiang; Zhao, Zhenwen

    2014-01-01

    Lipidomics is an emerging field, where the structures, functions and dynamic changes of lipids in cells, tissues or body fluids are investigated. Due to the vital roles of lipids in human physiological and pathological processes, lipidomics is attracting more and more attentions. However, because of the diversity and complexity of lipids, lipid analysis is still full of challenges. The recent development of methods for lipid extraction and analysis and the combination with bioinformatics technology greatly push forward the study of lipidomics. Among them, mass spectrometry (MS) is the most important technology for lipid analysis. In this review, the methodology based on MS for lipid analysis was introduced. It is believed that along with the rapid development of MS and its further applications to lipid analysis, more functional lipids will be identified as biomarkers and therapeutic targets and for the study of the mechanisms of disease. PMID:24921707

  14. In situ secondary ion mass spectrometry analysis

    SciTech Connect

    Groenewold, G.S.; Applehans, A.D.; Ingram, J.C.; Delmore, J.E.; Dahl, D.A.

    1993-01-01

    The direct detection of tributyl phosphate (TBP) on rocks using molecular beam surface analysis [MBSA or in situ secondary ion mass spectrometry (SIMS)] is demonstrated. Quantities as low as 250 ng were detected on basalt and sandstone with little or no sample preparation. Detection of TBP on soil has proven to be more problematic and requires further study. Ethylenediaminetetraacetic acid (EDTA) is more difficult to detect because it is very reactive with surfaces of interest. Nevertheless, it is possible to detect EDTA if the acidity of the surface is controlled. The detection of EDTA-metal complexes is currently an open question, but evidence is presented for the detection of ions arising from a EDTA-lead complex. Carboxylic acids (i.e., citric, ascorbic, malic, succinic, malonic, and oxalic) give characteristic SIM spectra, but their detection on sample surfaces awaits evaluation.

  15. Characterization of Microorganisms by MALDI Mass Spectrometry

    SciTech Connect

    Petersen, Catherine E.; Valentine, Nancy B.; Wahl, Karen L.

    2008-10-02

    Matrix-assisted laser desorption/ionization-time-of-flight mass spectrometry (MALDI-TOF MS) for characterization and analysis of microorganisms, specifically bacteria, is described here as a rapid screening tool. The objective of this technique is not comprehensive protein analysis of a microorganism but rather a rapid screening of the organism and the accessible protein pattern for characterization and distinction. This method is based on the ionization of the readily accessible and easily ionizable portion of the protein profile of an organism that is often characteristic of different bacterial species. The utility of this screening approach is yet to reach its full potential but could be applied to food safety, disease outbreak monitoring in hospitals, culture stock integrity and verification, microbial forensics or homeland security applications.

  16. Glass microfabricated nebulizer chip for mass spectrometry.

    PubMed

    Saarela, Ville; Haapala, Markus; Kostiainen, Risto; Kotiaho, Tapio; Franssila, Sami

    2007-05-01

    A microfluidic nebulizer chip for mass spectrometry is presented. It is an all-glass device which consists of fusion bonded Pyrex wafers with embedded flow channels and a nozzle at the chip edge. A platinum heater is located on the wafer backside. Fabrication of the chip is detailed, especially glass deep etching, wafer bonding, and metal patterning. Various process combinations of bonding and metallization have been considered (anodic bonding vs. fusion bonding; heater inside/outside channel; metallization before/after bonding; platinum lift-off vs. etching). The chip vaporizes the liquid sample (0.1-10 microL min(-1)) and mixes it with a nebulizer gas (ca. 100 sccm N2). Operating temperatures can go up to 500 degrees C ensuring efficient vaporization. Thermal insulation of the glass ensures low temperatures at the far end of the chip, enabling easy interconnections. PMID:17476387

  17. Recent trends in inorganic mass spectrometry

    SciTech Connect

    Smith, D.H.; Barshick, C.M.; Duckworth, D.C.; Riciputi, L.R.

    1996-10-01

    The field of inorganic mass spectrometry has seen substantial change in the author`s professional lifetime (over 30 years). Techniques in their infancy 30 years ago have matured; some have almost disappeared. New and previously unthought of techniques have come into being; some of these, such as ICP-MS, are reasonably mature now, while others have some distance to go before they can be so considered. Most of these new areas provide fertile fields for researchers, both in the development of new analytical techniques and by allowing fundamental studies to be undertaken that were previously difficult, impossible, or completely unforeseen. As full coverage of the field is manifestly impossible within the framework of this paper, only those areas with which the author has personal contact will be discussed. Most of the work originated in his own laboratory, but that of other laboratories is covered where it seemed appropriate.

  18. Characterisation of DEFB107 by mass spectrometry

    NASA Astrophysics Data System (ADS)

    McCullough, Bryan J.; Eastwood, Hayden; Clark, Dave J.; Polfer, Nick C.; Campopiano, Dominic J.; Dorin, Julia A.; Maxwell, Alison; Langley, Ross J.; Govan, John R. W.; Bernstein, Summer L.; Bowers, Michael T.; Barran, Perdita E.

    2006-05-01

    Mammalian defensins are small endogenous cationic proteins which form a class of antimicrobial peptides that is part of the innate immune response of all mammalian species [R. Lehrer, Nat. Rev. Microbiol. 2 (9) (2004) 727; T. Ganz, R.I. Lehrer, Curr. Opin. Immunol. 6 (4) (1994) 584] [1] and [2]. We have developed mass spectrometry based strategies for characterising the structure-activity relationship of defensins [D.J. Campopiano, D.J. Clarke, N.C. Polfer, P.E. Barran, R.J. Langley, J.R.W. Govan, A. Maxwell, J.R. Dorin, J. Biol. Chem. 279 (47) (2004) 48671; P.E. Barran, N.C. Polfer, D.J. Campopiano, D.J. Clarke, P.R.R. Langridge-Smith, R.J. Langley, J.R.W. Govan, A. Maxwell, J.R. Dorin, R.P. Millar, M.T. Bowers, Int. J. Mass Spectrom. 240 (2005) 273] [3] and [4], and here we present data obtained from a five cysteine containing [beta]-defensin, DEFB107. The synthetic product of this human defensin exists with a glutathione capping group, its oxidation state and disulphide connectivity have been determined via accurate mass measurements and peptide mass mapping respectively, and despite possessing three disulphide bridges, it does not fit the [beta]-defensin canonical motif. With the use of molecular modelling, we have generated candidate geometries to discern the influence of disulphide bridging on the overall tertiary structure of DEFB107. These are compared with experimental results from ion mobility measurements. Defensins display activity against a wide variety of pathogens including both gram-negative and gram-positive bacteria. Their mechanism of mode of action is unknown, but is believed to involve defensin aggregation at cell surfaces, followed by cell permeabilisation and hence deathE To probe this mechanism, the localisation of DEFB107 in synthetic vesicles was studied using H/D exchange and mass spectrometry. The results obtained are used to analyse the antimicrobial activity of DEFB107.

  19. Small system for tritium accelerator mass spectrometry

    DOEpatents

    Roberts, M.L.; Davis, J.C.

    1993-02-23

    Apparatus for ionizing and accelerating a sample containing isotopes of hydrogen and detecting the ratios of hydrogen isotopes contained in the sample is disclosed. An ion source generates a substantially linear ion beam including ions of tritium from the sample. A radio-frequency quadrupole accelerator is directly coupled to and axially aligned with the source at an angle of substantially zero degrees. The accelerator accelerates species of the sample having different mass to different energy levels along the same axis as the ion beam. A spectrometer is used to detect the concentration of tritium ions in the sample. In one form of the invention, an energy loss spectrometer is used which includes a foil to block the passage of hydrogen, deuterium and [sup 3]He ions, and a surface barrier or scintillation detector to detect the concentration of tritium ions. In another form of the invention, a combined momentum/energy loss spectrometer is used which includes a magnet to separate the ion beams, with Faraday cups to measure the hydrogen and deuterium and a surface barrier or scintillation detector for the tritium ions.

  20. Small system for tritium accelerator mass spectrometry

    DOEpatents

    Roberts, Mark L. (Livermore, CA); Davis, Jay C. (Livermore, CA)

    1993-01-01

    Apparatus for ionizing and accelerating a sample containing isotopes of hydrogen and detecting the ratios of hydrogen isotopes contained in the sample is disclosed. An ion source generates a substantially linear ion beam including ions of tritium from the sample. A radio-frequency quadrupole accelerator is directly coupled to and axially aligned with the source at an angle of substantially zero degrees. The accelerator accelerates species of the sample having different mass to different energy levels along the same axis as the ion beam. A spectrometer is used to detect the concentration of tritium ions in the sample. In one form of the invention, an energy loss spectrometer is used which includes a foil to block the passage of hydrogen, deuterium and .sup.3 He ions, and a surface barrier or scintillation detector to detect the concentration of tritium ions. In another form of the invention, a combined momentum/energy loss spectrometer is used which includes a magnet to separate the ion beams, with Faraday cups to measure the hydrogen and deuterium and a surface barrier or scintillation detector for the tritium ions.

  1. Improved Classification of Mass Spectrometry Database Search Results Using Newer

    E-print Network

    Zhu, Ji

    Improved Classification of Mass Spectrometry Database Search Results Using Newer Machine Learning spectrometry data is a current bottleneck in high throughput proteomics. In particular, the need to manually validate the results of mass spec- trometry database searching algorithms can be prohibi- tively time

  2. Explanatory Optimization of Protein Mass Spectrometry via Genetic Search

    E-print Network

    Fernandez, Thomas

    proteins are analyzed in isolation. Successful strategies for the analysis of intact proteins in complexExplanatory Optimization of Protein Mass Spectrometry via Genetic Search Seetharaman Vaidyanathan- sis of intact proteins by mass spectrometry is challenging, as many analytical factors influence

  3. Digital microfluidic sample preparation for biological mass spectrometry 

    E-print Network

    Stokes, Adam A.

    2011-06-27

    The use of mass spectrometry in the biosciences has undergone huge growth in re- cent years due to sustained effort in the development of new ionisation techniques, more powerful mass analysers and better bioinformatic ...

  4. Single-protein nanomechanical mass spectrometry in real time

    PubMed Central

    Hanay, M.S.; Kelber, S.; Naik, A.K.; Chi, D.; Hentz, S.; Bullard, E.C.; Colinet, E.; Duraffourg, L.; Roukes, M.L.

    2012-01-01

    Nanoelectromechanical systems (NEMS) resonators can detect mass with exceptional sensitivity. Previously, mass spectra from several hundred adsorption events were assembled in NEMS-based mass spectrometry using statistical analysis. Here, we report the first realization of single-molecule NEMS-based mass spectrometry in real time. As each molecule in the sample adsorbs upon the NEMS resonator, its mass and the position-of-adsorption are determined by continuously tracking two driven vibrational modes of the device. We demonstrate the potential of multimode NEMS-based mass spectrometry by analyzing IgM antibody complexes in real-time. NEMS-MS is a unique and promising new form of mass spectrometry: it can resolve neutral species, provides resolving power that increases markedly for very large masses, and allows acquisition of spectra, molecule-by-molecule, in real-time. PMID:22922541

  5. Present and future prospects of accelerator mass spectrometry

    SciTech Connect

    Kutschera, W.

    1987-04-01

    Accelerator Mass Spectrometry (AMS) has become a powerful technique for measuring extremely low abundances (10/sup -10/ to 10/sup -15/ relative to stable isotopes) of long-lived radioisotopes with half-lives in the range from 10/sup 2/ to 10/sup 8/ years. With a few exceptions, tandem accelerators turned out to be the most useful instruments for AMS measurements. Both natural (mostly cosmogenic) and man-made (anthropogenic) radioisotopes are studied with this technique. In some cases very low concentrations of stable isotope are also measured. Applications of AMS cover a large variety of fields including anthropology, archaeology, oceanography, hydrology, climatology, volcanology, minerals exploration, cosmochemistry, meteoritics, glaciology, sedimentary processes, geochronology, environmental physics, astrophysics, nuclear and particle physics. Present and future prospects of AMS are discussed as an interplay between the continuous development of new techniques and the investigation of problems in the above mentioned fields. Typical factors to be considered are energy range and type of accelerator, and the possibilities of dedicated versus partial use of new or existing accelerators.

  6. Measuring doubly 13C-substituted ethane by mass spectrometry

    NASA Astrophysics Data System (ADS)

    Clog, M.; Ling, C.; Eiler, J. M.

    2012-12-01

    Ethane (C2H6) is present in non-negligible amounts in most natural gas reservoirs and is used to produce ethylene for petrochemical industries. It is one of the by-products of lipid metabolism and is the arguably simplest molecule that can manifest multiple 13C substitutions. There are several plausible controls on the relative abundances of 13C2H6 in natural gases: thermodynamically controlled homogeneous isotope exchange reactions analogous to those behind carbonate clumped isotope thermometry; inheritance from larger biomolecules that under thermal degradation to produce natural gas; mixing of natural gases that differ markedly in bulk isotopic composition; or combinations of these and/or other, less expected fractionations. There is little basis for predicting which of these will dominate in natural samples. Here, we focus on an analytical techniques that will provide the avenue for exploring these phenomena. The method is based on high-resolution gas source isotope ratio mass spectrometry, using the Thermo 253-Ultra (a new prototype mass spectrometer). This instrument achieves the mass resolution (M/? M) up to 27,000, permitting separation of the isobaric interferences of potential contaminants and isotopologues of an analtye or its fragments which share a cardinal mass. We present techniques to analyze several isotopologues of molecular and fragment ions of C2H6. The critical isobaric separations for our purposes include: discrimination of 13C2H6 from 13C12CDH5 at mass 32 and separation of the 13CH3 fragment from 12CH4 at mass 16, both requiring at least a mass resolution of 20000 to make an adequate measurement. Other obvious interferences are either cleanly separated (e.g., O2, O) or accounted for by peak-stripping (CH3OH on mass 32 and NH2 on mass 16). We focus on a set of measurements which constrain: the doubly-substituted isotopologue, 13C2H6, and the 13CH3/12CH3 ratio of the methyl fragment, which constrains the bulk ? 13C. Similar methods can be used to measure the D/H ratio, among other species. The precision on the ? 13C is better than 0.25 permil (1 s.e.) on the CH3 fragment. Calculating ? 13C and ? D simultaneously on the intact isotopologues on masses 30 to 32 yields precisions of respectfully 0.2 and 4 permil (1 s.e.). Ratios of mass 32 to mass 30 species are measured to better than +/-0.7 per mil (1 s.e.). The corresponding precision on ? 13C2H6 (defined as 1000 * ((13C2H6/C2H6)measured/(13C2H6/C2H6)stochastic)-1)) is +/-0.85 per mil (1 s.e.). All precision reflects counting statistics and can be improved with longer counting times. Accuracy determinations are underway.

  7. Applications of Mass Spectrometry to Lipids and Membranes

    PubMed Central

    Harkewicz, Richard; Dennis, Edward A.

    2012-01-01

    Lipidomics, a major part of metabolomics, constitutes the detailed analysis and global characterization, both spatial and temporal, of the structure and function of lipids (the lipidome) within a living system. As with proteomics, mass spectrometry has earned a central analytical role in lipidomics, and this role will continue to grow with technological developments. Currently, there exist two mass spectrometry-based lipidomics approaches, one based on a division of lipids into categories and classes prior to analysis, the “comprehensive lipidomics analysis by separation simplification” (CLASS), and the other in which all lipid species are analyzed together without prior separation, shotgun. In exploring the lipidome of various living systems, novel lipids are being discovered, and mass spectrometry is helping characterize their chemical structure. Deuterium exchange mass spectrometry (DXMS) is being used to investigate the association of lipids and membranes with proteins and enzymes, and imaging mass spectrometry (IMS) is being applied to the in situ analysis of lipids in tissues. PMID:21469951

  8. US Food and Drug Administration Perspectives on Clinical Mass Spectrometry.

    PubMed

    Lathrop, Julia Tait; Jeffery, Douglas A; Shea, Yvonne R; Scholl, Peter F; Chan, Maria M

    2016-01-01

    Mass spectrometry-based in vitro diagnostic devices that measure proteins and peptides are underutilized in clinical practice, and none has been cleared or approved by the Food and Drug Administration (FDA) for marketing or for use in clinical trials. One way to increase their utilization is through enhanced interactions between the FDA and the clinical mass spectrometry community to improve the validation and regulatory review of these devices. As a reference point from which to develop these interactions, this article surveys the FDA's regulation of mass spectrometry-based devices, explains how the FDA uses guidance documents and standards in the review process, and describes the FDA's previous outreach to stakeholders. Here we also discuss how further communication and collaboration with the clinical mass spectrometry communities can identify opportunities for the FDA to provide help in the development of mass spectrometry-based devices and enhance their entry into the clinic. PMID:26553791

  9. Evaluation of TASTEX task H: measurement of plutonium isotopic abundances by gamma-ray spectrometry

    SciTech Connect

    Gunnink, R.; Prindle, A.L.; Asakura, Y.; Masui, J.; Ishiguro, N.; Kawasaki, A.; Kataoka, S.

    1981-10-01

    This report describes a computer-based gamma spectrometer system that was developed for measuring isotopic and total plutonium concentrations in nitric acid solutions. The system was installed at the Tokai reprocessing plant where it is undergoing testing and evaluation as part of the Tokai Advanced Safeguards Exercise (TASTEX). Objectives of TASTEX Task H, High-Resolution Gamma Spectrometer for Plutonium Isotopic Analysis, the methods and equipment used, the installation and calibration of the system, and the measurements obtained from several reprocessing campaigns are discussed and described. In general, we find that measurements for gamma spectroscopy agree well with those of mass spectrometry and of other chemical analysis. The system measures both freshly processed plutonium from the product accountability tank and aged plutonium solutions from storage tanks. 14 figures, 15 tables.

  10. A Century of Progress in Molecular Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    McLafferty, Fred W.

    2011-07-01

    The first mass spectrum of a molecule was measured by J.J. Thomson in 1910. Mass spectrometry (MS) soon became crucial to the study of isotopes and atomic weights and to the development of atomic weapons for World War II. Its notable applications to molecules began with the quantitative analysis of light hydrocarbons during World War II. When I joined the Dow Chemical Company in 1950, MS was not favored by organic chemists. This situation improved only with an increased understanding of gaseous ion chemistry, which was obtained through the use of extensive reference data. Gas chromatography-MS was developed in 1956, and tandem MS was first used a decade later. In neutralization-reionization MS, an unusual, unstable species is prepared by ion-beam neutralization and characterized by reionization. Electrospray ionization of a protein mixture produces its corresponding ionized molecules. In top-down proteomics, ions from an individual component can be mass separated and subjected to collision-activated and electron-capture dissociation to provide extensive sequence information.

  11. Toward laser ablation Accelerator Mass Spectrometry of actinides

    SciTech Connect

    R. C. Pardo; F. G. Kondev; S. Kondrashev; C. Nair; T. Palchan; R. Scott; D. Seweryniak; R. Vondrasek; M. Paul; P. Collon; C. Deibel; M. Salvatores; G. Palmiotti; J. Berg; J. Fonnesbeck; G. Imel

    2013-01-01

    A project to measure neutron capture cross sections of a number of actinides in a reactor environment by Accelerator Mass Spectrometry (AMS) at the ATLAS facility of Argonne National Laboratory is underway. This project will require the precise and accurate measurement of produced actinide isotopes in many (>30) samples irradiated in the Advanced Test Reactor at Idaho National Laboratory with neutron fluxes having different energy distributions. The AMS technique at ATLAS is based on production of highlycharged positive ions in an electron cyclotron resonance (ECR) ion source followed by acceleration in the ATLAS linac and mass-to-charge (m/q) measurement at the focus of the Fragment Mass Analyzer. Laser ablation was selected as the method of feeding the actinide material into the ion source because we expect it will have higher efficiency and lower chamber contamination than either the oven or sputtering techniques, because of a much narrower angular distribution of emitted material. In addition, a new multi-sample holder/changer to allow quick change between samples and a computer-controlled routine allowing fast tuning of the accelerator for different beams, are being developed. An initial test run studying backgrounds, detector response, and accelerator scaling repeatability was conducted in December 2010. The project design, schedule, and results of the initial test run to study backgrounds are discussed.

  12. Radionuclide measurements by accelerator mass spectrometry at Arizona

    NASA Astrophysics Data System (ADS)

    Jull, A. J. T.; Donahue, D. J.; Zabel, T. H.

    Over the past years, Tandem Accelerator Mass Spectrometry (TAMS) has become established as an important method for radionuclide analysis. In the Arizona system the accelerator is operated at a thermal voltage of 1.8MV for C-14 analysis, and 1.6 to 2MV for Be-10. Samples are inserted into a cesium sputter ion source in solid form. Negative ions sputtered from the target are accelerated to about 25kV, and the injection magnet selects ions of a particular mass. Ions of the 3+ charge state, having an energy of about 9MeV are selected by an electrostatic deflector, surviving ions pass through two magnets, where only ions of the desired mass-energy product are selected. The final detector is a combination ionization chamber to measure energy loss (and hence, Z), and a silicon surface-barrier detector which measures residual energy. After counting the trace iosotope for a fixed time, the injected ions are switched to the major isotope used for normalization. These ions are deflected into a Faraday cup after the first high-energy magnet. Repeated measurements of the isotope ratio of both sample and standards results in a measurement of the concentration of the radionuclide. Recent improvements in sample preparation for C-14 make preparation of high-beam current graphite targets directly from CO2 feasible. Except for some measurements of standards and backgrounds for Be-10 measurements to date have been on C-14. Although most results have been in archaeology and quaternary geology, studies have been expanded to include cosmogenic C-14 in meteorites. The data obtained so far tend to confirm the antiquity of Antarctic meteorites from the Allan Hills site. Data on three samples of Yamato meteorites gave terrestrial ages of between about 3 and 22 thousand years.

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

    DOEpatents

    Chen, Xian

    2006-10-24

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

  14. Identification of Unknown Contaminants in Water Samples from ISS Employing Liquid Chromatography/Mass Spectrometry/Mass Spectrometry

    NASA Technical Reports Server (NTRS)

    Rutz, Jeffrey A.; Schultz, John R.

    2008-01-01

    Mass Spectrometry/Mass Spectrometry (MS/MS) is a powerful technique for identifying unknown organic compounds. For non-volatile or thermally unstable unknowns dissolved in liquids, liquid chromatography/mass spectrometry/mass spectrometry (LC/MS/MS) is often the variety of MS/MS used for the identification. One type of LC/MS/MS that is rapidly becoming popular is time-of-flight (TOF) mass spectrometry. This technique is now in use at the Johnson Space Center for identification of unknown nonvolatile organics in water samples from the space program. An example of the successful identification of one unknown is reviewed in detail in this paper. The advantages of time-of-flight instrumentation are demonstrated through this example as well as the strategy employed in using time-of-flight data to identify unknowns.

  15. Determination of trace elements and correction of mass spectral interferences in superalloy analyzed by glow discharge mass spectrometry.

    PubMed

    Xing, Yu; Xiaojia, Li; Haizhou, Wang

    2008-01-01

    Mass spectral interference was investigated systematically during the determination of trace elements in superalloy by glow discharge mass spectrometry (GD-MS); moreover the main mass spectral interference and interference level of isotopes were provided in detail. According to the mass spectral interference of elements, different methods were selected for interference correction. The effects of mass spectral interference were removed efficiently by using correction methods such as selecting isotopes without interference, matching sample matrices and deducing interference with multivariable linear regression. The determination results of three superalloy samples show that trace elements such as B, Mg, Ga, As, Ag, In, Sn, Sb, Te, Tl, Pb and Bi were determined successfully after interference correction. PMID:18756019

  16. Fractionation in position-specific isotope composition during vaporization of environmental pollutants measured with isotope ratio monitoring by ¹³C nuclear magnetic resonance spectrometry.

    PubMed

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

    2015-10-01

    Isotopic fractionation of pollutants in terrestrial or aqueous environments is a well-recognized means by which to track different processes during remediation. As a complement to the common practice of measuring the change in isotope ratio for the whole molecule using isotope ratio monitoring by mass spectrometry (irm-MS), position-specific isotope analysis (PSIA) can provide further information that can be exploited to investigate source and remediation of soil and water pollutants. Position-specific fractionation originates from either degradative or partitioning processes. We show that isotope ratio monitoring by (13)C NMR (irm-(13)C NMR) spectrometry can be effectively applied to methyl tert-butylether, toluene, ethanol and trichloroethene to obtain this position-specific data for partitioning. It is found that each compound exhibits characteristic position-specific isotope fractionation patterns, and that these are modulated by the type of evaporative process occurring. Such data should help refine models of how remediation is taking place, hence back-tracking to identify pollutant sources. PMID:26123718

  17. Mass spectrometry of atmospheric pressure plasmas

    NASA Astrophysics Data System (ADS)

    Große-Kreul, S.; Hübner, S.; Schneider, S.; Ellerweg, D.; von Keudell, A.; Matej?ík, S.; Benedikt, J.

    2015-08-01

    Atmospheric pressure non-equilibrium plasmas (APPs) are effective source of radicals, metastables and a variety of ions and photons, ranging into the vacuum UV spectral region. A detailed study of these species is important to understand and tune desired effects during the interaction of APPs with solid or liquid materials in industrial or medical applications. In this contribution, the opportunities and challenges of mass spectrometry for detection of neutrals and ions from APPs, fundamental physical phenomena related to the sampling process and their impact on the measured densities of neutrals and fluxes of ions, will be discussed. It is shown that the measurement of stable neutrals and radicals requires a proper experimental design to reduce the beam-to-background ratio, to have little beam distortion during expansion into vacuum and to carefully set the electron energy in the ionizer to avoid radical formation through dissociative ionization. The measured ion composition depends sensitively on the degree of impurities present in the feed gas as well as on the setting of the ion optics used for extraction of ions from the expanding neutral-ion mixture. The determination of the ion energy is presented as a method to show that the analyzed ions are originating from the atmospheric pressure plasma.

  18. Applications of graphene in mass spectrometry.

    PubMed

    Kong, Xianglei; Huang, Yi

    2014-07-01

    This paper reviews the up-to-date research about the applications of graphene and its related materials in the field of mass spectrometry (MS). Due to its large surface area, delocalized pi-electrons, thermal conductivity, stability and rich interaction chemistry, graphene has been widely used in MS-based analytical chemistry. Graphene-based materials were applied as very effective matrixes or surfaces for many kinds of organic molecules in laser desorption/ionization (LDI) MS analysis. Many advantages of this novel matrix have been proved, which included: low interference ions from matrix itself, good reproducibility, high salt tolerance and so on. The unique properties of graphene also make it a superior sorbent used in solid-phase extraction (SPE). Further development of online SPE methods based on graphene coupling directly with LDI-MS, GC-MS and LC-MS greatly simplifies the MS-based analytical procedure for complex samples and makes the corresponding high-throughput and automatic analysis performable. Their applications as a platform in proteolysis for the rapid identification of proteins have been also developed. In addition, graphene was found to be a unique precursor for the generation of large-sized carbon cluster anions in the gas phase. Finally, the possible challenges and future perspectives in their applications in MS are discussed too. PMID:24757942

  19. Mass Spectrometry of Nanoparticles is Different

    NASA Astrophysics Data System (ADS)

    Liang, C.-K.; Eller, M. J.; Verkhoturov, S. V.; Schweikert, Emile A.

    2015-08-01

    Secondary ion mass spectrometry, SIMS, is a method of choice for the characterization of nanoparticles, NPs. For NPs with large surface-to-volume ratios, heterogeneity is a concern. Assays should thus be on individual nano-objects rather than an ensemble of NPs; however, this may be difficult or impossible. This limitation can be side-stepped by probing a large number of dispersed NPs one-by-one and recording the emission from each NP separately. A large collection of NPs will likely contain subsets of like-NPs. The experimental approach is to disperse the NPs and hit an individual NP with a single massive cluster (e.g., C-60, Au-400). At impact energies of ~1 keV/atom, they generate notable secondary ion (SI) emission. Examination of small NPs (?20 nm in diameter) shows that the SI emission is size-dependent and impacts are not all equivalent. Accurate identification of the type of impact is key for qualitative assays of core or outer shell composition. For quantitative assays, the concept of effective impacts is introduced. Selection of co-emitted ejecta combined with rejection (anticoincidence) of substrate ions allows refining chemical information within the projectile interaction volume. Last, to maximize the SI signal, small NPs (?5 nm in diameter) can be examined in the transmission mode where the SI yields are enhanced ~10-fold over those in the (conventional) reflection direction. Future endeavors should focus on schemes acquiring SIs, electrons, and photons concurrently.

  20. Mass Spectrometry of Nanoparticles is Different.

    PubMed

    Liang, C-K; Eller, M J; Verkhoturov, S V; Schweikert, Emile A

    2015-08-01

    Secondary ion mass spectrometry, SIMS, is a method of choice for the characterization of nanoparticles, NPs. For NPs with large surface-to-volume ratios, heterogeneity is a concern. Assays should thus be on individual nano-objects rather than an ensemble of NPs; however, this may be difficult or impossible. This limitation can be side-stepped by probing a large number of dispersed NPs one-by-one and recording the emission from each NP separately. A large collection of NPs will likely contain subsets of like-NPs. The experimental approach is to disperse the NPs and hit an individual NP with a single massive cluster (e.g., C-60, Au-400). At impact energies of ~1 keV/atom, they generate notable secondary ion (SI) emission. Examination of small NPs (?20 nm in diameter) shows that the SI emission is size-dependent and impacts are not all equivalent. Accurate identification of the type of impact is key for qualitative assays of core or outer shell composition. For quantitative assays, the concept of effective impacts is introduced. Selection of co-emitted ejecta combined with rejection (anticoincidence) of substrate ions allows refining chemical information within the projectile interaction volume. Last, to maximize the SI signal, small NPs (?5 nm in diameter) can be examined in the transmission mode where the SI yields are enhanced ~10-fold over those in the (conventional) reflection direction. Future endeavors should focus on schemes acquiring SIs, electrons, and photons concurrently. PMID:25944367

  1. Signatures for Mass Spectrometry Data Quality

    PubMed Central

    2015-01-01

    Ensuring data quality and proper instrument functionality is a prerequisite for scientific investigation. Manual quality assurance is time-consuming and subjective. Metrics for describing liquid chromatography mass spectrometry (LC–MS) data have been developed; however, the wide variety of LC–MS instruments and configurations precludes applying a simple cutoff. Using 1150 manually classified quality control (QC) data sets, we trained logistic regression classification models to predict whether a data set is in or out of control. Model parameters were optimized by minimizing a loss function that accounts for the trade-off between false positive and false negative errors. The classifier models detected bad data sets with high sensitivity while maintaining high specificity. Moreover, the composite classifier was dramatically more specific than single metrics. Finally, we evaluated the performance of the classifier on a separate validation set where it performed comparably to the results for the testing/training data sets. By presenting the methods and software used to create the classifier, other groups can create a classifier for their specific QC regimen, which is highly variable lab-to-lab. In total, this manuscript presents 3400 LC–MS data sets for the same QC sample (whole cell lysate of Shewanella oneidensis), deposited to the ProteomeXchange with identifiers PXD000320–PXD000324. PMID:24611607

  2. 3D Imaging by Mass Spectrometry: A New Frontier

    PubMed Central

    Seeley, Erin H.; Caprioli, Richard M.

    2012-01-01

    Summary Imaging mass spectrometry can generate three-dimensional volumes showing molecular distributions in an entire organ or animal through registration and stacking of serial tissue sections. Here we review the current state of 3D imaging mass spectrometry as well as provide insights and perspectives on the process of generating 3D mass spectral data along with a discussion of the process necessary to generate a 3D image volume. PMID:22276611

  3. New high temperature plasmas and sample introduction systems for analytical atomic emission and mass spectrometry

    SciTech Connect

    Montaser, A.

    1992-01-01

    New high temperature plasmas and new sample introduction systems are explored for rapid elemental and isotopic analysis of gases, solutions, and solids using mass spectrometry and atomic emission spectrometry. Emphasis was placed on atmospheric pressure He inductively coupled plasmas (ICP) suitable for atomization, excitation, and ionization of elements; simulation and computer modeling of plasma sources with potential for use in spectrochemical analysis; spectroscopic imaging and diagnostic studies of high temperature plasmas, particularly He ICP discharges; and development of new, low-cost sample introduction systems, and examination of techniques for probing the aerosols over a wide range. Refs., 14 figs. (DLC)

  4. INTERLABORATORY COMPARISON OF MASS SPECTROMETRIC METHODS FOR LEAD ISOTOPES AND TRACE ELEMENTS IN NIST SRM 1400 BONE ASH

    EPA Science Inventory

    The results of an interlaboratory comparison are reported for he lead isotope composition and for trace element concentrations in NIST SRM 1400 Bone Ash obtained using quadrupole and magnetic-sector inductively coupled plasma mass spectrometry (ICP-MS) and (for the Pb isotopes on...

  5. Mass Spectrometry for Characterizing Plant Cell Wall Polysaccharides

    PubMed Central

    Bauer, Stefan

    2012-01-01

    Mass spectrometry is a selective and powerful technique to obtain identification and structural information on compounds present in complex mixtures. Since it requires only small sample amount it is an excellent tool for researchers interested in detecting changes in composition of complex carbohydrates of plants. This mini-review gives an overview of common mass spectrometry techniques applied to the analysis of plant cell wall carbohydrates. It presents examples in which mass spectrometry has been used to elucidate the structure of oligosaccharides derived from hemicelluloses and pectins and illustrates how information on sequence, linkages, branching, and modifications are obtained from characteristic fragmentation patterns. PMID:22645587

  6. Secondary Ion Mass Spectrometry for Mg Tracer Diffusion: Issues and Solutions

    SciTech Connect

    Tuggle, Jay; Giordani, Andrew; Kulkarni, Nagraj S; Warmack, Robert J Bruce; Coffey, Kevin; Sohn, Yong Ho; HunterJr., Jerry

    2014-01-01

    A Secondary Ion Mass Spectrometry (SIMS) method has been developed to measure stable Mg isotope tracer diffusion. This SIMS method was then used to calculate Mg self- diffusivities and the data was verified against historical data measured using radio tracers. The SIMS method has been validated as a reliable alternative to the radio-tracer technique for the measurement of Mg self-diffusion coefficients and can be used as a routine method for determining diffusion coefficients.

  7. Mass Spectrometry Continuous Two-Channel Time-of-Flight Mass

    E-print Network

    Zare, Richard N.

    Mass Spectrometry Continuous Two-Channel Time-of-Flight Mass Spectrometric Detection, and Richard N. Zare* Time-of-flight mass spectrometry (TOFMS) is a widely used technique that is recognized and potentially the mass resolution if the flight path is shortened. In conventional TOFMS, packets of ions

  8. Transition of Iodine Analysis to Accelerator Mass Spectrometry

    SciTech Connect

    M. L. Adamic; J. E. Olson; D. D. Jenson; J. G. Eisenmenger; M. G. Watrous

    2012-09-01

    This NA 22 funded research project investigated the transition of iodine isotopic analyses from thermal ionization mass spectrometry (TIMS) to an accelerator mass spectrometry (AMS) system. Previous work (Fiscal Year 2010) had demonstrated comparable data from TIMS and AMS. With AMS providing comparable data with improved background levels and vastly superior sample throughput, improvement in the sample extraction from environmental sample matrices was needed to bring sample preparation throughput closer to the operation level of the instrument. Previous research used an extraction chemistry that was not optimized for yield or refined for reduced labor to prove the principle. This research was done to find an extraction with better yield using less labor per sample to produce a sample ready for the AMS instrument. An extraction method using tetramethyl ammonium hydroxide (TMAH) was developed for removal of iodine species from high volume air filters. The TMAH with gentle heating was superior to the following three extraction methods: ammonium hydroxide aided by sonication, acidic and basic extraction aided by microwave, and ethanol mixed with sodium hydroxide. Taking the iodine from the extraction solvent to being ready for AMS analysis was accomplished by a direct precipitation, as well as, using silver wool to harvest the iodine from the TMAH. Portions of the same filters processed in FY 2010 were processed again with the improved extraction scheme followed by successful analysis by AMS at the Swiss Federal Institute of Technology. The data favorably matched the data obtained in 2010. The time required for analysis has been reduced over the aqueous extraction/AMS approach developed in FY 2010. For a hypothetical batch of 30 samples, the AMS methodology is about 10 times faster than the traditional gas phase chemistry and TIMS analysis. As an additional benefit, background levels for the AMS method are about 1000 times lower than TIMS. This results from the fundamental mechanisms of ionization in the AMS system and which produces a beneficial cleanup of molecular interferences. Continued clean operation of the extraction process was demonstrated through blank analysis included with all sample sets analyzed. INL work showed improvement on the first year’s demonstration of AMS vs. TIMS. An improved extraction of high volume air filters followed by isotopic analysis by AMS, can be used successfully to make iodine measurements with results comparable to those obtained by filter combustion and TIMS analysis. More progress on the conversion from an extract solution to an AMS sample ready for analysis is still needed. Although the preparation scheme through AMS is already at a higher performing thoughput than TIMS, the chemical preparation cannot match the instrument capability for number of samples per day without further development.

  9. Transition of Iodine Analysis to Accelerator Mass Spectrometry

    SciTech Connect

    J. E. Delmore

    2010-09-01

    Funding was received from NA-22 to investigate transitioning iodine isotopic analyses to an accelerator mass spectrometry (AMS) system. The present method uses gas-phase chemistry followed by thermal ionization mass spectrometry (TIMS). It was anticipated that the AMS approach could provide comparable data, with improved background levels and superior sample throughput. An aqueous extraction method was developed for removal of iodine species from high-volume air filters. Ethanol and sodium hydroxide, plus heating and ultrasonic treatment, were used to successfully extract iodine from loaded high-volume air filters. Portions of the same filters were also processed in the traditional method and analyzed by TIMS for comparison. Aliquot parts of the aqueous extracts were analyzed by AMS at the Swiss Federal Institute of Technology. Idaho National Laboratory (INL) personnel visited several AMS laboratories in the US, Spain, and Switzerland. Experience with AMS systems from several manufacturers was gained, and relationships were developed with key personnel at the laboratories. Three batches of samples were analyzed in Switzerland, and one in Spain. Results show that the INL extraction method successfully extracted enough iodine from high-volume air filters to allow AMS analysis. Comparison of the AMS and TIMS data is very encouraging; while the TIMS showed about forty percent more atoms of 129I, the 129/127 ratios tracked each other very well between the two methods. The time required for analysis is greatly reduced for the aqueous extraction/AMS approach. For a hypothetical batch of thirty samples, the AMS methodology is about five times faster than the traditional gas-phase chemistry and TIMS analysis. As an additional benefit, background levels for the AMS method are about 1000 times lower than for TIMS. This results from the fundamental mechanisms of ionization in the AMS system and cleanup of molecular interferences. We showed that an aqueous extraction of high-volume air filters, followed by isotopic analysis by AMS, can be used successfully to make iodine measurements with results comparable to those obtained by filter combustion and TIMS analysis.

  10. Determination of femtogram quantities of protactinium in geologic samples by thermal ionization mass spectrometry

    SciTech Connect

    Pickett, D.A.; Murrell, M.T.; Williams, R.W. )

    1994-04-01

    We describe a procedure for measurement of [sup 231]Pa in geologic samples by isotope dilution thermal ionization mass spectrometry, using [sup 233]Pa as a spike isotope, which provides marked improvements in precision and sample size relative to established decay counting techniques. This method allows determination of as little as a few tens of femtograms of [sup 231]Pa (approximately 10[sup 3] atoms) with a conservative estimated uncertainty of [+-]1% (95% confidence level). Applications of [sup 231]Pa-[sup 235]U systematics to uranium-series geochemistry and geochronology should be greatly enhanced by this approach. 31 refs., 4 figs., 1 tab.

  11. Ion and neutral mass spectrometry of the isotopic composition of Titan's upper atmosphere: Implications for the atmospheric dynamics and photochemistry, and the evolution of the major species over geological time scales

    NASA Astrophysics Data System (ADS)

    Mandt, Kathleen E.

    The atmosphere of Titan, Saturn's largest moon, is an analog for the Earth's atmosphere in the distant past when life first emerged, and may also be used to study the distant future when the abundance of water in the atmosphere may be reduced by photochemical loss processes associated with climate change. This Dissertation investigates the evolution of Titan's atmosphere utilizing measurements of the stable isotope ratios in molecular nitrogen and methane. The Cassini Ion Neutral Mass Spectrometer (INMS) measures the composition of the ionosphere and neutral atmosphere as it flies through the atmosphere, approaching altitudes as low as 950 km above the surface. INMS measurements of the 14N/15N in N2 as a function of altitude for 30 Titan flybys are compared, using a basic diffusion model, to the Huygens Gas Chromatograph Mass Spectrometer (GCMS) measurement of the 14N/15N in N2 on the surface. This comparison provides the input parameters needed to extrapolate the INMS measurements of 12C/13C in CH4 from the upper atmosphere to the surface where the ratio is within the range of expected primordial values. Although the 12C/13C at Titan is close to the primordial value, escape and photochemistry fractionate the isotope ratio over time. This suggests that methane has been present in Titan's atmosphere for no more than one billion years. A cross-calibration of INMS ion densities with the electron densities measured by the Cassini Radio Plasma Wave Spectrometer (RPWS) constrains the energy response of INMS and provides a new approach for determining the densities of ions in Titan's ionosphere. These ion densities validate an updated coupled Ion-Neutral-Thermal model that constrains the fractionation of the nitrogen isotopes due to photochemistry. Modeling the evolution of the nitrogen isotopes over geological times scales based on chemistry and escape limits the initial 14N/15N to a heavier ratio than the 14N/ 15N observed in the Earth's atmosphere. The methodologies developed for this Dissertation are relevant not only to Titan, but also to Earth. They can be used to evaluate dynamics and photochemistry of the nitrogen isotopes in the upper atmosphere and to define future missions to study the composition of the Earth's thermosphere.

  12. Mass spectrometric measurements of the isotopic anatomies of molecules (Invited)

    NASA Astrophysics Data System (ADS)

    Eiler, J. M.; Krumwiede, D.; Schlueter, H.

    2013-12-01

    Site-specific and multiple isotopic substitutions in molecular structures potentially provide an extraordinarily rich set of constraints on their sources, conditions of formation, reaction and transport histories, and perhaps other issues. Examples include carbonate ';clumped isotope' thermometry, clumped isotope measurements of CO2, O2, and, recently, methane, ethane and N2O; site-specific 15N measurements in N2O and 13C and D analyses of fatty acids, sugars, cellulose, food products, and, recently, n-alkanes. Extension of the principles behind these tools to the very large number of isotopologues of complex molecules could potentially lead to new uses of isotope chemistry, similar to proteomics, metabolomics and genomics in their complexity and depth of detail (';isotomics'?). Several technologies are potentially useful for this field, including ';SNIF-NMR', gas source mass spectrometry and IR absorption spectroscopy. However, all well established methods have restrictive limits in the sizes of samples, types of analyzes, and the sorts of isotopologues that can be measured with useful precision. We will present an overview of several emerging instruments and techniques of high-resolution gas source mass spectrometry that may enable study of a large proportion of the isotopologues of a wide range of volatile and semi-volatile compounds, including many organics, with precisions and sample sizes suitable for a range of applications. A variety of isotopologues can be measured by combining information from the Thermo 253 Ultra (a new high resolution, multi-collector gas source mass spectrometer) and the Thermo DFS (a very high resolution single collector, but used here on a novel mode to achieve ~per mil precision ratio measurements), sometimes supplemented by conventional bulk isotopic measurements. It is possible to design methods in which no one of these sources of data meaningfully constrain abundances of specific isotopologues, but their combination fully and precisely constrains a large number. We have assembled a suite of instruments (including the prototype of the Ultra, and a modified version of the DFS that is capable of dual inlet analyses) that make it logistically straightforward to perform such multi-instrument analyses. Examples will be presented documenting the accuracy of these techniques for systems that are independently well known (e.g., isotopologues of methane), and the precision and internal consistency of results for larger, more complex molecules (e.g., a suite of singly and doubly substituted isotopologues of hexane and other moderate-molecular-weight organics).

  13. Radiocarbon detection by ion charge exchange mass spectrometry

    NASA Astrophysics Data System (ADS)

    Hotchkis, Michael; Wei, Tao

    2007-06-01

    A method for detection of radiocarbon at low levels is described and the results of tests are presented. We refer to this method as ion charge exchange mass spectrometry (ICE-MS). The ICE-MS instrument is a two stage mass spectrometer. In the first stage, molecular interferences which would otherwise affect radiocarbon detection at mass 14 are eliminated by producing high charge state ions directly in the ion source (charge state ?2). 14N interference is eliminated in the second stage by converting the beam to negative ions in a charge exchange cell. The beam is mass-analysed at each stage. We have built a test apparatus consisting of an electron cyclotron resonance ion source and a pair of analysing magnets with a charge exchange cell in between, followed by an electrostatic analyser to improve the signal to background ratio. With this apparatus we have measured charge exchange probabilities for (Cn+ ? C-) from 4.5 to 40.5 keV (n = 1-3). We have studied the sources of background including assessment of limits for nitrogen interference by searching for negative ions from charge exchange of 14N ions. Our system has been used to detect 14C in enriched samples of CO2 gas with 14C/12C isotopic ratio down to the 10-9 level. Combined with a measured sample consumption rate of 4 ng/s, this corresponds to a capability to detect transient signals containing only a few ?Bq of 14C activity, such as may be obtained from chromatographic separation. The method will require further development to match the sensitivity of AMS with a gas ion source; however, even in its present state its sensitivity is well suited to tracer studies in biomedical research and drug development.

  14. Liquid Chromatography-Mass Spectrometry Quantitation: Applications and Methods

    E-print Network

    Baird, Serena Nicole

    2013-12-31

    , and environmental hazards. Liquid chromatography-mass spectrometry (LC-MS) is capable of completing such tasks using a variety of quantitative methods. In Chapter 1, these methods are presented with regards to chemical warfare agent studies. External calibration...

  15. Molecular Beam Mass Spectrometry (MBMS) (Revised) (Fact Sheet)

    SciTech Connect

    Not Available

    2011-07-01

    This fact sheet provides information about Molecular Beam Mass Spectrometry (MBMS) capabilities and applications at NREL's National Bioenergy Center. NREL has six MBMS systems that researchers and industry partners can use to understand thermochemical biomass conversion and biomass composition recalcitrance.

  16. Signal variation in single particle aerosol mass spectrometry

    E-print Network

    Wissner-Gross, Zachary Daniel

    2007-01-01

    Rapid and accurate detection of airborne micro-particles is currently an important problem in national security. One approach to such detection, bioaerosol mass spectrometry (BAMS), is currently under development at Lawrence ...

  17. Photodissociation mass spectrometry: New tools for characterization of biological molecules

    PubMed Central

    Brodbelt, Jennifer S.

    2014-01-01

    Photodissociation mass spectrometry combines the ability to activate and fragment ions using photons with the sensitive detection of the resulting product ions by mass spectrometry. The resulting combination affords a versatile tool for characterization of biological molecules. The scope and breadth of photodissociation mass spectrometry have increased substantially over the past decade as new research groups have entered the field and developed a number of innovative applications that illustrate the ability of photodissociation to produce rich fragmentation patterns, to cleave bonds selectively, and to target specific molecules based on incorporation of chromophores. This review focuses on many of the key developments in photodissociation mass spectrometry over the past decade with a particular emphasis on its applications to biological molecules. PMID:24481009

  18. Laser mass spectrometry for DNA sequencing, disease diagnosis, and fingerprinting

    SciTech Connect

    Winston Chen, C.H.; Taranenko, N.I.; Zhu, Y.F.; Chung, C.N.; Allman, S.L.

    1997-03-01

    Since laser mass spectrometry has the potential for achieving very fast DNA analysis, the authors recently applied it to DNA sequencing, DNA typing for fingerprinting, and DNA screening for disease diagnosis. Two different approaches for sequencing DNA have been successfully demonstrated. One is to sequence DNA with DNA ladders produced from Snager`s enzymatic method. The other is to do direct sequencing without DNA ladders. The need for quick DNA typing for identification purposes is critical for forensic application. The preliminary results indicate laser mass spectrometry can possibly be used for rapid DNA fingerprinting applications at a much lower cost than gel electrophoresis. Population screening for certain genetic disease can be a very efficient step to reducing medical costs through prevention. Since laser mass spectrometry can provide very fast DNA analysis, the authors applied laser mass spectrometry to disease diagnosis. Clinical samples with both base deletion and point mutation have been tested with complete success.

  19. Recent applications of mass spectrometry in forensic toxicology

    NASA Astrophysics Data System (ADS)

    Foltz, Rodger L.

    1992-09-01

    This review encompasses applications of mass spectrometry reported during the years 1989, 1990 and 1991 for the analysis of cannabinoids, cocaine, opiates, amphetamines, lysergic acid diethylamide (LSD), and their metabolites in physiological specimens.

  20. Isoelectric Trapping and Mass Spectrometry: Tools for Proteomics 

    E-print Network

    Cologna, Stephanie Marie

    2012-02-14

    Mass spectrometry (MS) has played a major role in the proteomic analysis of an array of biological samples. Even so, inherent limitations exist such as sample complexity and the dynamic range. In an attempt to overcome ...

  1. Characterization of phenolic resins with thermogravimetry-mass spectrometry

    SciTech Connect

    Chang, Cherng; Tackett, J.R.

    1990-01-01

    As part of an advanced material research program, thermogravimetry-mass spectrometry (TG-MS) analysis of a phenolic resin was carried out recently for the study of the curing of the prepolymer, solvent extraction, and carbonization of the polymer at high temperature in inert atmosphere. These steps are critical to the quality of the produced advanced material. In addition to TG-MS, several other complementary techniques were also employed for the analysis of the phenolic resin prepolymer and its curing and thermal degradation products. These techniques include pyrolysis-gas chromatography-mass spectrometry, direct insertion probe-mass spectrometry and gas chromatography-mass spectrometry. 7 refs., 5 figs., 3 tabs.

  2. Mass Spectrometry of Membrane Proteins: A Focus on Aquaporins

    PubMed Central

    Schey, Kevin L.; Grey, Angus C.; Nicklay, Joshua J.

    2015-01-01

    Membrane proteins are abundant, critically important biomolecules that conduct essential functions in all cells and are the targets of a significant number of therapeutic drugs. However, the analysis of their expression, modification, protein–protein interactions, and structure by mass spectrometry has lagged behind similar studies of soluble proteins. Here we review the limitations to analysis of integral membrane and membrane-associated proteins and highlight advances in sample preparation and mass spectrometry methods that have led to the successful analysis of this protein class. Advances in the analysis of membrane protein posttranslational modification, protein–protein interaction, protein structure, and tissue distributions by imaging mass spectrometry are discussed. Furthermore, we focus our discussion on the application of mass spectrometry for the analysis of aquaporins as a prototypical integral membrane protein and how advances in analytical methods have revealed new biological insights into the structure and function of this family of proteins. PMID:23394619

  3. Laser mass spectrometry for DNA sequencing, disease diagnosis, and fingerprinting

    NASA Astrophysics Data System (ADS)

    Chen, C. H. Winston; Taranenko, N. I.; Zhu, Y. F.; Chung, C. N.; Allman, S. L.

    1997-05-01

    Since laser mass spectrometry has the potential for achieving very fast DNA analysis, we recently applied it to DNA sequencing, DNA typing for fingerprinting, and DNA screening for disease diagnosis. Two different approaches for sequencing DNA have been successfully demonstrated. One is to sequence DNA with DNA ladders produced from Sanger's enzymatic method. The other is to do direct sequencing without DNA ladders. The need for quick DNA typing for identification purposes is critical for forensic application. Our preliminary results indicate laser mass spectrometry can possible be used for rapid DNA fingerprinting applications at a much lower cost than gel electrophoresis. Population screening for certain genetic disease can be a very efficient step to reducing medical costs through prevention. Since laser mass spectrometry can provide very fast DNA analysis, we applied laser mass spectrometry to disease diagnosis. Clinical samples with both base deletion and point mutation have been tested with complete success.

  4. Environmental Mass Spectrometry: Emerging Contaminants and Current Issues (2010 Review)

    EPA Science Inventory

    This biennial review covers developments in environmental mass spectrometry for emerging environmental contaminants over the period of 2008-2009. A few significant references that appeared between January and February 2010 are also included. Analytical Chemistry’s current polic...

  5. Tools for investigating cellular signaling networks by mass spectrometry

    E-print Network

    Curran, Timothy Gordon

    2014-01-01

    Mass spectrometry has become the tool of choice for proteomics. Its unrivaled coverage and reproducibility has positioned it head and shoulders above competing techniques for analyzing protein expression post-translational ...

  6. Inductively coupled plasma mass spectrometry and electrospray mass spectrometry for speciation analysis: applications and instrumentation

    NASA Astrophysics Data System (ADS)

    Rosen, Amy L.; Hieftje, Gary M.

    2004-02-01

    To gain an understanding of the function, toxicity and distribution of trace elements, it is necessary to determine not only the presence and concentration of the elements of interest, but also their speciation, by identifying and characterizing the compounds within which each is present. For sensitive detection of compounds containing elements of interest, inductively coupled plasma mass spectrometry (ICP-MS) is a popular method, and for identification of compounds via determination of molecular weight, electrospray ionization mass spectrometry (ESI-MS) is gaining increasing use. ICP-MS and ESI-MS, usually coupled to a separation technique such as chromatography or capillary electrophoresis, have already been applied to a large number of research problems in such diverse fields as environmental chemistry, nutritional science, and bioinorganic chemistry, but a great deal of work remains to be completed. Current areas of research to which ICP-MS and ESI-MS have been applied are discussed, and the existing instrumentation used to solve speciation problems is described.

  7. Electron Transfer Dissociation Mass Spectrometry of Hemoglobin on Clinical Samples

    NASA Astrophysics Data System (ADS)

    Coelho Graça, Didia; Lescuyer, Pierre; Clerici, Lorella; Tsybin, Yury O.; Hartmer, Ralf; Meyer, Markus; Samii, Kaveh; Hochstrasser, Denis F.; Scherl, Alexander

    2012-10-01

    A mass spectrometry-based assay combining the specificity of selected reaction monitoring and the protein ion activation capabilities of electron transfer dissociation was developed and employed for the rapid identification of hemoglobin variants from whole blood without previous proteolytic cleavage. The analysis was performed in a robust ion trap mass spectrometer operating at nominal mass accuracy and resolution. Subtle differences in globin sequences, resulting with mass shifts of about one Da, can be unambiguously identified. These results suggest that mass spectrometry analysis of entire proteins using electron transfer dissociation can be employed on clinical samples in a workflow compatible with diagnostic applications.

  8. imzML: Imaging Mass Spectrometry Markup Language: A common data format for mass spectrometry imaging.

    PubMed

    Römpp, Andreas; Schramm, Thorsten; Hester, Alfons; Klinkert, Ivo; Both, Jean-Pierre; Heeren, Ron M A; Stöckli, Markus; Spengler, Bernhard

    2011-01-01

    Imaging mass spectrometry is the method of scanning a sample of interest and generating an "image" of the intensity distribution of a specific analyte. The data sets consist of a large number of mass spectra which are usually acquired with identical settings. Existing data formats are not sufficient to describe an MS imaging experiment completely. The data format imzML was developed to allow the flexible and efficient exchange of MS imaging data between different instruments and data analysis software.For this purpose, the MS imaging data is divided in two separate files. The mass spectral data is stored in a binary file to ensure efficient storage. All metadata (e.g., instrumental parameters, sample details) are stored in an XML file which is based on the standard data format mzML developed by HUPO-PSI. The original mzML controlled vocabulary was extended to include specific parameters of imaging mass spectrometry (such as x/y position and spatial resolution). The two files (XML and binary) are connected by offset values in the XML file and are unambiguously linked by a universally unique identifier. The resulting datasets are comparable in size to the raw data and the separate metadata file allows flexible handling of large datasets.Several imaging MS software tools already support imzML. This allows choosing from a (growing) number of processing tools. One is no longer limited to proprietary software, but is able to use the processing software which is best suited for a specific question or application. On the other hand, measurements from different instruments can be compared within one software application using identical settings for data processing. All necessary information for evaluating and implementing imzML can be found at http://www.imzML.org . PMID:21063949

  9. Chemical separation and mass spectrometry of Cr, Fe, Ni, Zn, and Cu in terrestrial and extraterrestrial materials using thermal ionization mass spectrometry.

    PubMed

    Yamakawa, Akane; Yamashita, Katsuyuki; Makishima, Akio; Nakamura, Eizo

    2009-12-01

    A sequential chemical separation technique for Cr, Fe, Ni, Zn, and Cu in terrestrial and extraterrestrial silicate rocks was developed for precise and accurate determination of elemental concentration by the isotope dilution method (ID). The technique uses a combination of cation-anion exchange chromatography and Eichrom nickel specific resin. The method was tested using a variety of matrixes including bulk meteorite (Allende), terrestrial peridotite (JP-1), and basalt (JB-1b). Concentrations of each element was determined by thermal ionization mass spectrometry (TIMS) using W filaments and a Si-B-Al type activator for Cr, Fe, Ni, and Zn and a Re filament and silicic acid-H3PO4 activator for Cu. The method can be used to precisely determine the concentrations of these elements in very small silicate samples, including meteorites, geochemical reference samples, and mineral standards for microprobe analysis. Furthermore, the Cr mass spectrometry procedure developed in this study can be extended to determine the isotopic ratios of 53Cr/52Cr and 54Cr/52Cr with precision of approximately 0.05epsilon and approximately 0.10epsilon (1epsilon = 0.01%), respectively, enabling cosmochemical applications such as high precision Mn-Cr chronology and investigation of nucleosynthetic isotopic anomalies in meteorites. PMID:19886654

  10. Subcellular analysis by laser ablation electrospray ionization mass spectrometry

    SciTech Connect

    Vertes, Akos; Stolee, Jessica A; Shrestha, Bindesh

    2014-12-02

    In various embodiments, a method of laser ablation electrospray ionization mass spectrometry (LAESI-MS) may generally comprise micro-dissecting a cell comprising at least one of a cell wall and a cell membrane to expose at least one subcellular component therein, ablating the at least one subcellular component by an infrared laser pulse to form an ablation plume, intercepting the ablation plume by an electrospray plume to form ions, and detecting the ions by mass spectrometry.

  11. 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

  12. High-performance MEMS square electrode quadrupole mass filters for chip-scale mass spectrometry

    E-print Network

    Cheung, Kerry

    We report exciting experimental data from a low-cost, high-performance square electrode quadrupole mass filter with integrated ion optics intended for chips-cale mass spectrometry. The device showed a mass range of 650 amu ...

  13. RAPID DETERMINATION OF ACTINIDES IN URINE BY INDUCTIVELY-COUPLED PLASMA MASS SPECTROMETRY AND ALPHA SPECTROMETRY: A HYBRID APPROACH

    SciTech Connect

    Maxwell, S.; Jones, V.

    2009-05-27

    A new rapid separation method that allows separation and preconcentration of actinides in urine samples was developed for the measurement of longer lived actinides by inductively coupled plasma mass spectrometry (ICP-MS) and short-lived actinides by alpha spectrometry; a hybrid approach. This method uses stacked extraction chromatography cartridges and vacuum box technology to facilitate rapid separations. Preconcentration, if required, is performed using a streamlined calcium phosphate precipitation. Similar technology has been applied to separate actinides prior to measurement by alpha spectrometry, but this new method has been developed with elution reagents now compatible with ICP-MS as well. Purified solutions are split between ICP-MS and alpha spectrometry so that long- and short-lived actinide isotopes can be measured successfully. The method allows for simultaneous extraction of 24 samples (including QC samples) in less than 3 h. Simultaneous sample preparation can offer significant time savings over sequential sample preparation. For example, sequential sample preparation of 24 samples taking just 15 min each requires 6 h to complete. The simplicity and speed of this new method makes it attractive for radiological emergency response. If preconcentration is applied, the method is applicable to larger sample aliquots for occupational exposures as well. The chemical recoveries are typically greater than 90%, in contrast to other reported methods using flow injection separation techniques for urine samples where plutonium yields were 70-80%. This method allows measurement of both long-lived and short-lived actinide isotopes. 239Pu, 242Pu, 237Np, 243Am, 234U, 235U and 238U were measured by ICP-MS, while 236Pu, 238Pu, 239Pu, 241Am, 243Am and 244Cm were measured by alpha spectrometry. The method can also be adapted so that the separation of uranium isotopes for assay is not required, if uranium assay by direct dilution of the urine sample is preferred instead. Multiple vacuum box locations may be set-up to supply several ICP-MS units with purified sample fractions such that a high sample throughput may be achieved, while still allowing for rapid measurement of short-lived actinides by alpha spectrometry.

  14. Classification of Mass spectrometry data using principal components analysis, Bayesian

    E-print Network

    Browne, William J.

    the bulk of the ions produced in the mass spectrometer carry a unit positive charge, the value mClassification of Mass spectrometry data using principal components analysis, Bayesian MCMC Components 4. MCMC method 5. Peak finding algorithm 6. Cross validation 7. Further Work 2 #12;Mass

  15. THE APPLICATION OF MASS SPECTROMETRY TO THE STUDY OF MICROORGANISMS

    EPA Science Inventory

    The purpose of this research project is to use state-of-the-art mass spectrometric techniques, such as electrospray ionization (ESI) and matrix assisted laser desorption ionization (MALDI) mass spectrometry (MS), to provide "protein mass fingerprinting" and protein sequencing i...

  16. Aluminum-26 as a biological tracer using accelerator mass spectrometry

    NASA Astrophysics Data System (ADS)

    Flarend, Richard Edward

    1997-06-01

    The development of accelerator mass spectrometry (AMS) has provided a practical method of detection for the only isotope of aluminum suitable as a tracer, 26Al. The use of 26Al as a tracer for aluminum has made possible the study of aluminum metabolism and the pharmacokinetics of aluminum-containing drugs at physiological levels. An overview of the various advantages of using 26Al as a tracer for aluminum and a general description of the AMS technique as applied to bio-medical applications is given. To illustrate the versatility of 26Al as a tracer for aluminum, 26Al studies of the past several years are discussed briefly. In addition, Two novel investigations dealing with 26Al-labeled drugs will be presented in more detail. In one of these studies, it was found that 26Al from aluminum hydroxide and aluminum phosphate vaccine adjuvants appeared in the blood just one hour after intramuscular injection. This is a surprising result since the currently held theory of how adjuvants work assumes that adjuvants remain insoluble and hold the antigen at the injection site for a long period of time. In another project, 26Al-labeled antiperspirants are being characterized by combining AMS with traditional analytical and chromatographic techniques. Future directions for this and other possible studies are discussed.

  17. Quantitative Proteomics Using Ultralow Flow Capillary Electrophoresis–Mass Spectrometry

    PubMed Central

    2015-01-01

    In this work, we evaluate the incorporation of an ultralow flow interface for coupling capillary electrophoresis (CE) and mass spectrometry (MS), in combination with reversed-phase high-pressure liquid chromatography (HPLC) fractionation as an alternate workflow for quantitative proteomics. Proteins, extracted from a SILAC (stable isotope labeling by amino acids in cell culture) labeled and an unlabeled yeast strain were mixed and digested enzymatically in solution. The resulting peptides were fractionated using RP-HPLC and analyzed by CE–MS yielding a total of 28?538 quantified peptides that correspond to 3?272 quantified proteins. CE–MS analysis was performed using a neutral capillary coating, providing the highest separation efficiency at ultralow flow conditions (<10 nL/min). Moreover, we were able to demonstrate that CE–MS is a powerful method for the identification of low-abundance modified peptides within the same sample. Without any further enrichment strategies, we succeeded in quantifying 1?371 phosphopeptides present in the CE–MS data set and found 49 phosphopeptides to be differentially regulated in the two yeast strains. Including acetylation, phosphorylation, deamidation, and oxidized forms, a total of 8?106 modified peptides could be identified in addition to 33?854 unique peptide sequences found. The work presented here shows the first quantitative proteomics approach that combines SILAC labeling with CE–MS analysis. PMID:25839223

  18. Penning trap mass measurements on nobelium isotopes

    NASA Astrophysics Data System (ADS)

    Dworschak, M.; Block, M.; Ackermann, D.; Audi, G.; Blaum, K.; Droese, C.; Eliseev, S.; Fleckenstein, T.; Haettner, E.; Herfurth, F.; Heßberger, F. P.; Hofmann, S.; Ketelaer, J.; Ketter, J.; Kluge, H.-J.; Marx, G.; Mazzocco, M.; Novikov, Yu. N.; Plaß, W. R.; Popeko, A.; Rahaman, S.; Rodríguez, D.; Scheidenberger, C.; Schweikhard, L.; Thirolf, P. G.; Vorobyev, G. K.; Wang, M.; Weber, C.

    2010-06-01

    The Penning trap mass spectrometer SHIPTRAP at GSI Darmstadt allows accurate mass measurements of radionuclides, produced in fusion-evaporation reactions and separated by the velocity filter SHIP from the primary beam. Recently, the masses of the three nobelium isotopes No252-254 were determined. These are the first direct mass measurements of transuranium elements, which provide new anchor points in this region. The heavy nuclides were produced in cold-fusion reactions by irradiating a PbS target with a Ca48 beam, resulting in production rates of the nuclei of interest of about one atom per second. In combination with data from decay spectroscopy our results are used to perform a new atomic-mass evaluation in this region.

  19. Penning trap mass measurements on nobelium isotopes

    SciTech Connect

    Dworschak, M.; Block, M.; Ackermann, D.; Herfurth, F.; Hessberger, F. P.; Hofmann, S.; Vorobyev, G. K.; Audi, G.; Blaum, K.; Droese, C.; Marx, G.; Schweikhard, L.; Eliseev, S.; Ketter, J.; Fleckenstein, T.; Haettner, E.; Plass, W. R.; Scheidenberger, C.; Ketelaer, J.; Kluge, H.-J.

    2010-06-15

    The Penning trap mass spectrometer SHIPTRAP at GSI Darmstadt allows accurate mass measurements of radionuclides, produced in fusion-evaporation reactions and separated by the velocity filter SHIP from the primary beam. Recently, the masses of the three nobelium isotopes {sup 252-254}No were determined. These are the first direct mass measurements of transuranium elements, which provide new anchor points in this region. The heavy nuclides were produced in cold-fusion reactions by irradiating a PbS target with a {sup 48}Ca beam, resulting in production rates of the nuclei of interest of about one atom per second. In combination with data from decay spectroscopy our results are used to perform a new atomic-mass evaluation in this region.

  20. Distribution of Foliar-applied Boron Measured by Spark-source Mass Spectrometry and Laser-probe Mass Spectrography

    PubMed Central

    Chamel, André R.; Andréani, Anne-Marie; Eloy, Jean-François

    1981-01-01

    The distribution of foliar-applied boron ([10B]boric acid) in radish (Raphanus sativus L.) was studied using for analysis of the stable isotopes a technique allowing a high sensitivity: spark-source mass spectrometry. Boron was recovered in the nontreated aerial parts and in the roots; however, the greatest fraction was in the treated leaf. It was possible with a laser-probe mass spectrograph to show that boron was not superficially located in the treated area but was present in tissues at all levels of depth considered. Images PMID:16661693

  1. Mass spectrometry imaging and profiling of single cells

    PubMed Central

    Lanni, Eric J.; Rubakhin, Stanislav S.; Sweedler, Jonathan V.

    2012-01-01

    Mass spectrometry imaging and profiling of individual cells and subcellular structures provide unique analytical capabilities for biological and biomedical research, including determination of the biochemical heterogeneity of cellular populations and intracellular localization of pharmaceuticals. Two mass spectrometry technologies—secondary ion mass spectrometry (SIMS) and matrix assisted laser desorption ionization mass spectrometry (MALDI MS)—are most often used in micro-bioanalytical investigations. Recent advances in ion probe technologies have increased the dynamic range and sensitivity of analyte detection by SIMS, allowing two- and three-dimensional localization of analytes in a variety of cells. SIMS operating in the mass spectrometry imaging (MSI) mode can routinely reach spatial resolutions at the submicron level; therefore, it is frequently used in studies of the chemical composition of subcellular structures. MALDI MS offers a large mass range and high sensitivity of analyte detection. It has been successfully applied in a variety of single-cell and organelle profiling studies. Innovative instrumentation such as scanning microprobe MALDI and mass microscope spectrometers enable new subcellular MSI measurements. Other approaches for MS-based chemical imaging and profiling include those based on near-field laser ablation and inductively-coupled plasma MS analysis, which offer complementary capabilities for subcellular chemical imaging and profiling. PMID:22498881

  2. Secondary Ion Mass Spectrometry Imaging of Dictyostelium discoideum Aggregation Streams

    SciTech Connect

    Debord, J. Daniel; Smith, Donald F.; Anderton, Christopher R.; Heeren, Ronald M.; Pasa-Tolic, Ljiljana; Gomer, Richard H.; Fernandez-Lima, Francisco A.

    2014-06-09

    High resolution imaging mass spectrometry could become a valuable tool for cell and developmental biology, but both, high spatial and mass spectral resolution are needed to enable this. In this report, we employed Bi3 bombardment time-of-flight (Bi3 ToF-SIMS) and C60 bombardment Fourier transform ion cyclotron resonance secondary ion mass spectrometry (C60 FTICR-SIMS) to image Dictyostelium discoideum aggregation streams. Nearly 300 lipid species were identified from the aggregation streams. High resolution mass spectrometry imaging (FTICR-SIMS) enabled the generation of multiple molecular ion maps at the nominal mass level and provided good coverage for fatty acyls, prenol lipids, and sterol lipids. The comparison of Bi3 ToF-SIMS and C60 FTICR-SIMS suggested that while the first provides fast, high spatial resolution molecular ion images, the chemical complexity of biological samples warrants the use of high resolution analyzers for accurate ion identification.

  3. [Determination of glyphosate and aminomethylphosphonic acid residues in foods using high performance liquid chromatography-mass spectrometry/mass spectrometry].

    PubMed

    Li, Bo; Deng, Xiaojun; Guo, Dehua; Jin, Shuping

    2007-07-01

    A method for the determination of glyphosate (PMG) and aminomethylphosphonic acid (AMPA) residues in plant products, such as rice, wheat, vegetables, fruits and tea, pig and chicken muscles, aquatic products, chestnut, honey, etc., was developed using high performance liquid chromatography coupled to tandem mass spectrometry (HPLC-MS/MS). In this method, PMG and AMPA were extracted with water from samples, defatted using an extraction step with dichloromethane, and purified using a cation-exchange (CAX) solid phase extraction cartridge. Then, these were derived using fluorenylmethylchloroformate (FMOC-Cl) in borate buffer for subsequent HPLC-MS/MS analysis. Isotope-labeled PMG 1, 2(13)- C(15) N was used as the internal standard for the quantitative analysis of two residues. For all samples, the recoveries ranged from 80.0% to 104% and the relative standard deviations (RSDs) ranged from 6.7% to 18.2%. The limit of quantification (LOQ) was determined to be 0.05 mg/kg with a linear range of 0.20-10 microg/L. It is demonstrated that this method is reliable and sensitive for the analysis of PMG and APMA with low concentrations in foods. PMID:17970103

  4. Comparative analysis of 1-phenyl-2-propanone (P2P), an amphetamine-type stimulant precursor, using stable isotope ratio mass spectrometry: presented in part as a poster at the 2nd meeting of the Joint European Stable Isotope User Meeting (JESIUM), Giens, France, September 2008.

    PubMed

    Schneiders, S; Holdermann, T; Dahlenburg, R

    2009-06-01

    The isotope ratios of amphetamine type stimulants (ATS) depend as well on the precursor as the synthetic pathway. For clandestine production of amphetamine and methamphetamine, 1-phenyl-2-propanone (P2P, benzylmethylketone) is a commonly used precursor. Our aim was to determine the variation of the isotope ratios within precursor samples of one manufacturer and to compare seized samples of unknown sources to these values. delta13C(V-PDB), delta2H(V-SMOW) and delta118O(V-SMOW) isotope ratios were determined using elemental analysis (EA) and gas chromatography (GC) coupled toan isotope ratio mass spectrometer (IRMS). The comparison of all seized samples to the data of the samples of one manufacturer revealed considerable differences. The results show that IRMS provides a high potential in differentiating between precursors from different manufacturers for the clandestine production of ATS and identifying corresponding sources. PMID:19606587

  5. Limitations of Mass Spectrometry-Based Peptidomic Approaches

    NASA Astrophysics Data System (ADS)

    Fricker, Lloyd D.

    2015-08-01

    Mass spectrometry-based peptidomic approaches are powerful techniques to detect and identify the peptide content of biological samples. The present study investigated the limitations of peptidomic approaches using trimethylammonium butyrate isotopic tags to quantify relative peptide levels and Mascot searches to identify peptides. Data were combined from previous studies on human cell lines or mouse tissues. The combined databases contain 2155 unique peptides ranging in mass from 444 to 8765 Da, with the vast majority between 1 and 3 kDa. The amino acid composition of the identified peptides generally reflected the frequency in the Eukaryotic proteome with the exception of Cys, which was not present in any of the identified peptides in the free-SH form but was detected at low frequency as a disulfide with Cys residues, a disulfide with glutathione, or as S-cyanocysteine. To test if the low detection rate of peptides smaller than 500 Da, larger than 3 kDa, or containing Cys was a limitation of the peptidomics procedure, tryptic peptides of known proteins were processed for peptidomics using the same approach used for human cell lines and mouse tissues. The identified tryptic peptides ranged from 516 to 2418 Da, whereas the theoretical digest ranged from 217 to 7559 Da. Peptides with Cys were rarely detected and, if present, the Cys was usually modified S-cyanocysteine. Additionally, peptides with mono- and di-iodo Tyr and His were identified. Taken together, there are limitations of peptidomic techniques, and awareness of these limitations is important to properly use and interpret results.

  6. Limitations of Mass Spectrometry-Based Peptidomic Approaches.

    PubMed

    Fricker, Lloyd D

    2015-12-01

    Mass spectrometry-based peptidomic approaches are powerful techniques to detect and identify the peptide content of biological samples. The present study investigated the limitations of peptidomic approaches using trimethylammonium butyrate isotopic tags to quantify relative peptide levels and Mascot searches to identify peptides. Data were combined from previous studies on human cell lines or mouse tissues. The combined databases contain 2155 unique peptides ranging in mass from 444 to 8765 Da, with the vast majority between 1 and 3 kDa. The amino acid composition of the identified peptides generally reflected the frequency in the Eukaryotic proteome with the exception of Cys, which was not present in any of the identified peptides in the free-SH form but was detected at low frequency as a disulfide with Cys residues, a disulfide with glutathione, or as S-cyanocysteine. To test if the low detection rate of peptides smaller than 500 Da, larger than 3 kDa, or containing Cys was a limitation of the peptidomics procedure, tryptic peptides of known proteins were processed for peptidomics using the same approach used for human cell lines and mouse tissues. The identified tryptic peptides ranged from 516 to 2418 Da, whereas the theoretical digest ranged from 217 to 7559 Da. Peptides with Cys were rarely detected and, if present, the Cys was usually modified S-cyanocysteine. Additionally, peptides with mono- and di-iodo Tyr and His were identified. Taken together, there are limitations of peptidomic techniques, and awareness of these limitations is important to properly use and interpret results. Graphical Abstract ?. PMID:26305799

  7. Use of Mass spectrometry for imaging metabolites in plants

    SciTech Connect

    Lee, Young Jin; Perdian, David C.; Song, Zhihong; Yeung, Edward S.; Nikolau, Basil

    2012-03-27

    We discuss and illustrate recent advances that have been made to image the distribution of metabolites among cells and tissues of plants using different mass spectrometry technologies. These technologies include matrix-assisted laser desorption ionization, desorption electrospray ionization, and secondary ion mass spectrometry. These are relatively new technological applications of mass spectrometry and they are providing highly spatially resolved data concerning the cellular distribution of metabolites. We discuss the advantages and limitations of each of these mass spectrometric methods, and provide a description of the technical barriers that are currently limiting the technology to the level of single-cell resolution. However, we anticipate that advances in the next few years will increase the resolving power of the technology to provide unprecedented data on the distribution of metabolites at the subcellular level, which will increase our ability to decipher new knowledge concerning the spatial organization of metabolic processes in plants.

  8. Use of mass spectrometry for imaging metabolites in plants

    SciTech Connect

    Lee, Young-Jin; Perdian, David; Song, Zhihong; Yeung, Edward; Nikolau, Basil

    2012-03-27

    We discuss and illustrate recent advances that have been made to image the distribution of metabolites among cells and tissues of plants using different mass spectrometry technologies. These technologies include matrix-assisted laser desorption ionization, desorption electrospray ionization, and secondary ion mass spectrometry. These are relatively new technological applications of mass spectrometry and they are providing highly spatially resolved data concerning the cellular distribution of metabolites. We discuss the advantages and limitations of each of these mass spectrometric methods, and provide a description of the technical barriers that are currently limiting the technology to the level of single-cell resolution. However, we anticipate that advances in the next few years will increase the resolving power of the technology to provide unprecedented data on the distribution of metabolites at the subcellular level, which will increase our ability to decipher new knowledge concerning the spatial organization of metabolic processes in plants.

  9. Applications of Mass Spectrometry to Structural Analysis of Marine Oligosaccharides

    PubMed Central

    Lang, Yinzhi; Zhao, Xia; Liu, Lili; Yu, Guangli

    2014-01-01

    Marine oligosaccharides have attracted increasing attention recently in developing potential drugs and biomaterials for their particular physical and chemical properties. However, the composition and sequence analysis of marine oligosaccharides are very challenging for their structural complexity and heterogeneity. Mass spectrometry (MS) has become an important technique for carbohydrate analysis by providing more detailed structural information, including molecular mass, sugar constituent, sequence, inter-residue linkage position and substitution pattern. This paper provides an overview of the structural analysis based on MS approaches in marine oligosaccharides, which are derived from some biologically important marine polysaccharides, including agaran, carrageenan, alginate, sulfated fucan, chitosan, glycosaminoglycan (GAG) and GAG-like polysaccharides. Applications of electrospray ionization mass spectrometry (ESI-MS) are mainly presented and the general applications of matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) are also outlined. Some technical challenges in the structural analysis of marine oligosaccharides by MS have also been pointed out. PMID:24983643

  10. Laser desorption lamp ionization source for ion trap mass spectrometry

    E-print Network

    Zare, Richard N.

    Laser desorption lamp ionization source for ion trap mass spectrometry Qinghao Wu and Richard N. Zare* A two-step laser desorption lamp ionization source coupled to an ion trap mass spectrometer (LDLI-ITMS) has been constructed and characterized. The pulsed infrared (IR) output of an Nd:YAG laser (1064 nm

  11. Analysis of intact bacteria using rapid evaporative ionisation mass spectrometry.

    PubMed

    Strittmatter, Nicole; Jones, Emrys A; Veselkov, Kirill A; Rebec, Monica; Bundy, Jacob G; Takats, Zoltan

    2013-07-14

    An identification system for microorganisms based on recently developed rapid evaporative ionisation mass spectrometry (REIMS) is presented. Nine bacterial species cultured on various growth media were correctly identified to family-, genus-, and species-level based on their different mass spectral fingerprints using a cross-validated maximum margin criterion model. PMID:23736664

  12. Atmospheric Pressure Molecular Imaging by Infrared MALDI Mass Spectrometry

    E-print Network

    Vertes, Akos

    Atmospheric Pressure Molecular Imaging by Infrared MALDI Mass Spectrometry Yue Li, Bindesh Shrestha/fructose, and citric acid species around the embedded seeds. Infrared AP MALDI mass spectrometric imaging without Washington University, Washington, DC 20052 An atmospheric pressure (AP) MALDI imaging interface

  13. Decision treedriven tandem mass spectrometry for shotgun proteomics

    E-print Network

    Cai, Long

    -scale protein sequencing. Tandem mass spectrometry, the process of peptide ion dissociation followed by mass efforts use enzymatic digestion of complex protein mixtures to generate samples contain- ing thousands of peptides1­3. The resultant mixtures are rich in chemical diversity as the peptides vary in length, post

  14. Infrared Laser Ablation Atmospheric Pressure Photoionization Mass Spectrometry

    E-print Network

    Vertes, Akos

    Infrared Laser Ablation Atmospheric Pressure Photoionization Mass Spectrometry Anu Vaikkinen ablation atmo- spheric pressure photoionization (LAAPPI), a novel atmospheric pressure ion source for mass analytes are desolvated and ionized in the gas-phase by atmospheric pressure photoionization using a 10 e

  15. NEGATIVE-ION MASS SPECTROMETRY OF SULFONYLUREA HERBICIDES

    EPA Science Inventory

    Sulfonylurea herbicides have been studied using neg-ion desorption chem.-ionization (DCI) mass spectrometry (MS) and DCI-MS/MS techniques. Both {M-H]- and M.- ions were obsd. in the DCI mass spectra. The collisonally activated dissocn. (CAD) spectra were characteristic of the str...

  16. Mass spectrometry and hyphenated instruments in food analysis

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Mass spectrometry (MS) has come a long way since the record of the first mass spectra of a simple low molecular weight substance by J.J. Thomson in 1912. Especially over the past decades, MS has been the subject of many developments. Particularly, the hyphenation of MS to gas chromatography (GC) a...

  17. An investigation of the tyrothricin complex by tandem mass spectrometry

    NASA Astrophysics Data System (ADS)

    Barber, M.; Bell, D. J.; Morris, M. R.; Tetler, L. W.; Monaghan, J. J.; Morden, W. E.; Bycroft, B. W.; Green, B. N.

    1992-12-01

    Tandem mass spectrometry has been shown to be a powerful technique for determining the structures of biological compounds. This paper details the mass spectrometric methods employed to characterise the structural variations found within a mixture of cyclic decapeptides, tyrothricin, produced by the bacterium Bacillus brevis.

  18. Desorption electrospray ionization mass spectrometry of intact bacteria

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Desorption electrospray ionization (DESI) mass spectrometry (MS) was used to differentiate 7 bacterial species based on their measured DESI-mass spectral profile. Both Gram positive and Gram negative bacteria were tested and included Escherichia coli, Staphyloccocus aureus, Enterococcus sp., Bordete...

  19. Characterization of Thiolate-Protected Gold Nanoparticles by Mass Spectrometry

    PubMed Central

    Harkness, Kellen M.; Cliffel, David E.; McLean, John A.

    2014-01-01

    Thiolate-protected gold nanoparticles (AuNPs) are a highly versatile nanomaterial, with wide-ranging physical properties dependent upon the protecting thiolate ligands and gold core size. These nanoparticles serve as a scaffold for a diverse and rapidly increasing number of applications, extending from molecular electronics to vaccine development. Key to the development of such applications is the ability to quickly and precisely characterize synthesized AuNPs. While a unique set of challenges have inhibited the potential of mass spectrometry in this area, recent improvements have made mass spectrometry a dominant technique in the characterization of small AuNPs, specifically those with discrete sizes and structures referred to as monolayer-protected gold clusters (MPCs). The unique ability of mass spectrometry to analyze the protecting monolayer of the AuNP may cause it to become a major technique in the characterization of larger AuNPs. The development of mass spectrometry techniques for AuNP characterization has begun to reveal interesting new areas of research. This report is a discussion of the historical challenges in this field, the emerging techniques which aim to meet those challenges, and the future role of mass spectrometry in the growing field of thiolate-protected AuNPs. PMID:20419232

  20. DETERMINATION OF ELEMENTAL COMPOSITIONS BY HIGH RESOLUTION MASS SPECTROMETRY WITHOUT MASS CALIBRANTS

    EPA Science Inventory

    Widely applicable mass calibrants, including perfluorokerosene, are available for gas-phase introduction of analytes ionized by electron impact (EI) prior to analysis using high resolution mass spectrometry. Unfortunately, no all-purpose calibrants are available for recently dev...

  1. Comparison of chicken and pheasant ovotransferrin N-glycoforms via electrospray ionization mass spectrometry and liquid chromatography coupled with mass spectrometry.

    PubMed

    Jiang, Kuan; Wang, Chengjian; Sun, Yujiao; Liu, Yang; Zhang, Ying; Huang, Linjuan; Wang, Zhongfu

    2014-07-23

    Species-specific ovotransferrin features a highly conservative protein sequence, but it varies in the structure of the attached oligosaccharides, which may contribute to the differences observed in its bioactivity and nutritional value. Herein, chicken ovotransferrin (COT) and pheasant ovotransferrin (POT) isolated by repeated ethanol precipitation of egg white were digested with peptide N-glycosidase F to release N-glycans. The obtained N-glyans were isotopically labeled with aniline and analyzed via electrospray ionization mass spectrometry and online hydrophilic interaction liquid chromatography coupled with tandem mass spectrometry (HILIC-MS/MS). Relative quantitation based on isotopic aniline labeling and HILIC-MS/MS analysis revealed in detail the conspicuous difference between COT and POT in the abundance of their N-glycan compositions and isomers. In total, 16 COT N-glycans were observed, including 1 core structure (3.18%), 3 hybrid type (5.42%), and 12 complex type (91.40%), whereas 21 POT N-glycans were found, including 1 truncated structure (1.88%), 1 core structure (6.26%), 3 high mannose type (5.20%), 6 hybrid type (19.14%), and 10 complex type (67.52%). To our knowledge, this study is the first qualitative and quantitative comparison of COT and POT N-glycosylation patterns. These results suggest that POT has a different glycosylation pattern compared to that of COT and thus the effect of its glycosylation pattern on its bioactivity is worthy of further exploration. PMID:24998151

  2. A Developmental History of Polymer Mass Spectrometry

    ERIC Educational Resources Information Center

    Vergne, Matthew J.; Hercules, David M.; Lattimer, Robert P.

    2007-01-01

    The history of the development of mass spectroscopic methods used to characterize polymers is discussed. The continued improvements in methods and instrumentation will offer new and better ways for the mass spectral characterization of polymers and mass spectroscopy (MS) should be recognized as a complementary polymer characterization method along…

  3. Mass Spectrometry Analysis of Pseudomonas aeruginosa Treated with Azithromycin

    NASA Astrophysics Data System (ADS)

    Phelan, Vanessa V.; Fang, Jinshu; Dorrestein, Pieter C.

    2015-06-01

    In microbiology, changes in specialized metabolite production (cell-to-cell signaling metabolites, virulence factors, and natural products) are measured using phenotypic assays. However, advances in mass spectrometry-based techniques including imaging mass spectrometry (IMS) now allow researchers to directly visualize the production of specialized metabolites from microbial colony biofilms. In this study, a combination of IMS and liquid chromatography-tandem mass spectrometry (LC-MS/MS) was used to visualize the effect of the macrolide antibiotic azithromycin (AZM) on colony biofilms of Pseudomonas aeruginosa. Although previous research suggested that AZM may inhibit cell-to-cell signaling of P. aeruginosa and thereby reduce pathogenicity, we observed no clear decrease in specialized metabolite production.

  4. Mass spectrometry imaging for in situ kinetic histochemistry

    PubMed Central

    Louie, Katherine B.; Bowen, Benjamin P.; McAlhany, Stephanie; Huang, Yurong; Price, John C.; Mao, Jian-hua; Hellerstein, Marc; Northen, Trent R.

    2013-01-01

    Tissues are composed of diverse cell subpopulations each with distinct metabolic characteristics that influence overall behavior. Unfortunately, traditional histopathology imaging techniques are ‘blind’ to the spatially ordered metabolic dynamics within tissue. While mass spectrometry imaging enables spatial mapping of molecular composition, resulting images are only a static snapshot in time of molecules involved in highly dynamic processes; kinetic information of flux through metabolic pathways is lacking. To address this limitation, we developed kinetic mass spectrometry imaging (kMSI), a novel technique integrating soft desorption/ionization mass spectrometry with clinically accepted in vivo metabolic labeling of tissue with deuterium to generate images of kinetic information of biological processes. Applied to a tumor, kMSI revealed heterogeneous spatial distributions of newly synthesized versus pre-existing lipids, with altered lipid synthesis patterns distinguishing region-specific intratumor subpopulations. Images also enabled identification and correlation of metabolic activity of specific lipids found in tumor regions of varying grade. PMID:23584513

  5. Laser desorption mass spectrometry for biomolecule detection and its applications

    NASA Astrophysics Data System (ADS)

    Winston Chen, C. H.; Sammartano, L. J.; Isola, N. R.; Allman, S. L.

    2001-08-01

    During the past few years, we developed and used laser desorption mass spectrometry for biomolecule detections. Matrix-assisted laser desorption/ionization (MALDI) was successfully used to detect DNA fragments with the size larger than 3000 base pairs. It was also successfully used to sequence DNA with both enzymatic and chemical degradation methods to produce DNA ladders. We also developed MALDI with fragmentation for direct DNA sequencing for short DNA probes. Since laser desorption mass spectrometry for DNA detection has the advantages of fast speed and no need of labeling, it has a great potential for molecular diagnosis for disease and person identification by DNA fingerprinting. We applied laser desorption mass spectrometry to succeed in the diagnosis of cystic fibrosis and several other nerve degenerative diseases such as Huntington's disease. We also succeeded in demonstrating DNA typing for forensic applications.

  6. Accurate Quantitation of Dystrophin Protein in Human Skeletal Muscle Using Mass Spectrometry.

    PubMed

    Brown, Kristy J; Marathi, Ramya; Fiorillo, Alyson A; Ciccimaro, Eugene F; Sharma, Seema; Rowlands, David S; Rayavarapu, Sree; Nagaraju, Kanneboyina; Hoffman, Eric P; Hathout, Yetrib

    2012-12-18

    Quantitation of human dystrophin protein in muscle biopsies is a clinically relevant endpoint for both diagnosis and response to dystrophin-replacement therapies for dystrophinopathies. A robust and accurate assay would enable the use of dystrophin as a surrogate biomarker, particularly in exploratory Phase 2 trials. Currently available methods to quantitate dystrophin rely on immunoblot or immunohistochemistry methods that are not considered robust. Here we present a mass spectrometry based approach to accurately quantitate dystrophin protein in a total protein extract from human muscle biopsies. Our approach uses a combination of stable isotope labeled dystrophin as a spike-in standard, gel electrophoresis and high precision mass spectrometry to detect and quantitate multiple peptides of dystrophin within a complex protein mixture. The method was found highly reproducible and linear over a wide dynamic range, detecting as low as 5% of dystrophin relative to the normal amount in healthy individuals. PMID:23646235

  7. Direct analysis of samples by mass spectrometry: From elements to bio-molecules using laser ablation inductively couple plasma mass spectrometry and laser desorption/ionization mass spectrometry

    SciTech Connect

    Perdian, David C.

    2009-08-19

    Mass spectrometric methods that are able to analyze solid samples or biological materials with little or no sample preparation are invaluable to science as well as society. Fundamental research that has discovered experimental and instrumental parameters that inhibit fractionation effects that occur during the quantification of elemental species in solid samples by laser ablation inductively coupled plasma mass spectrometry is described. Research that determines the effectiveness of novel laser desorption/ionization mass spectrometric methods for the molecular analysis of biological tissues at atmospheric pressure and at high spatial resolution is also described. A spatial resolution is achieved that is able to analyze samples at the single cell level.

  8. 230Th-234U Age-Dating Uranium by Mass Spectrometry

    SciTech Connect

    Williams, R W; Gaffney, A M

    2012-04-18

    This is the standard operating procedure used by the Isotope Ratio Mass Spectrometry Group of the Chemical Sciences Division at LLNL for the preparation of a sample of uranium oxide or uranium metal for {sup 230}Th-{sup 234}U age-dating. The method described here includes the dissolution of a sample of uranium oxide or uranium metal, preparation of a secondary dilution, spiking of separate aliquots for uranium and thorium isotope dilution measurements, and purification of uranium and thorium aliquots for mass spectrometry. This SOP may be applied to uranium samples of unknown purity as in a nuclear forensic investigation, and also to well-characterized samples such as, for example, U{sub 3}O{sub 8} and U-metal certified reference materials. The sample of uranium is transferred to a quartz or PFA vial, concentrated nitric acid is added and the sample is heated on a hotplate at approximately 100 C for several hours until it dissolves. The sample solution is diluted with water to make the solution approximately 4 M HNO{sub 3} and hydrofluoric acid is added to make it 0.05 M HF. A secondary dilution of the primary uranium solution is prepared. Separate aliquots for uranium and thorium isotope dilution measurements are taken and spiked with {sup 233}U and {sup 229}Th, respectively. The spiked aliquot for uranium isotope dilution analysis is purified using EiChrom UTEVA resin. The spiked aliquot for thorium isotope dilution analysis is purified by, first, a 1.8 mL AG1x8 resin bed in 9 M HCl on which U adsorbs and Th passes through; second, adsorbing Th on a 1 mL AG1x8 resin bed in 8 M HNO{sub 3} and then eluting it with 9 M HCl followed by 0.1 M HCl + 0.005 M HF; and third, by passing the Th through a final 1.0 mL AG1x8 resin bed in 9 M HCl. The mass spectrometry is performed using the procedure 'Th and U Mass Spectrometry for {sup 230}Th-{sup 234}U Age Dating'.

  9. Laser electrospray mass spectrometry of adsorbed molecules at atmospheric pressure

    NASA Astrophysics Data System (ADS)

    Brady, John J.; Judge, Elizabeth J.; Simon, Kuriakose; Levis, Robert J.

    2010-02-01

    Atmospheric pressure mass analysis of solid phase biomolecules is performed using laser electrospray mass spectrometry (LEMS). A non-resonant femtosecond duration laser pulse vaporizes native samples at atmospheric pressure for subsequent electrospray ionization and transfer into a mass spectrometer. LEMS was used to detect a complex molecule (irinotecan HCl), a complex mixture (cold medicine formulation with active ingredients: acetaminophen, dextromethorphan HBr and doxylamine succinate), and a biological building block (deoxyguanosine) deposited on steel surfaces without a matrix molecule.

  10. Xenon purity analysis for EXO-200 via mass spectrometry

    E-print Network

    A. Dobi; C. Hall; S. Slutsky; Y. -R. Yen; B. Aharmin; M. Auger; P. S. Barbeau; C. Benitez-Medina; M. Breidenbach; B. Cleveland; R. Conley; J. Cook; S. Cook; I. Counts; W. Craddock; T. Daniels; C. G. Davis; J. Davis; R. deVoe; M. Dixit; M. J. Dolinski; K. Donato; W. Fairbank Jr.; J. Farine; P. Fierlinger; D. Franco; G. Giroux; R. Gornea; K. Graham; G. Gratta; C. Green; C. Hagemann; K. Hall; D. Hallman; C. Hargrove; S. Herrin; M. Hughes; J. Hodgson; F. Juget; A. Karelin; L. J. Kaufman; A. Kuchenkov; K. Kumar; D. S. Leonard; G. Lutter; D. Mackay; R. MacLellan; M. Marino; B. Mong; M. Montero Díez; P. Morgan; A. R. Müller; R. Neilson; A. Odian; K. O'Sullivan; A. Piepke; A. Pocar; C. Y. Prescott; K. Pushkin; A. Rivas; E. Rollin; P. C. Rowson; A. Sabourov; D. Sinclair; K. Skarpaas; V. Stekhanov; V. Strickland; M. Swift; K. Twelker; J. -L. Vuilleumier; J. -M. Vuilleumier; M. Weber; U. Wichoski; J. Wodin; J. D. Wright; L. Yang

    2011-09-06

    We describe purity measurements of the natural and enriched xenon stockpiles used by the EXO-200 double beta decay experiment based on a mass spectrometry technique. The sensitivity of the spectrometer is enhanced by several orders of magnitude by the presence of a liquid nitrogen cold trap, and many impurity species of interest can be detected at the level of one part-per-billion or better. We have used the technique to screen the EXO-200 xenon before, during, and after its use in our detector, and these measurements have proven useful. This is the first application of the cold trap mass spectrometry technique to an operating physics experiment.

  11. Direct Protocol for Ambient Mass Spectrometry Imaging on Agar Culture.

    PubMed

    Angolini, Célio Fernando F; Vendramini, Pedro Henrique; Araújo, Francisca D S; Araújo, Welington L; Augusti, Rodinei; Eberlin, Marcos N; de Oliveira, Luciana Gonzaga

    2015-07-01

    Herein we describe a new protocol that allows direct mass spectrometry imaging (IMS) of agar cultures. A simple sample dehydration leads to a thin solid agar, which enables the direct use of spray-based ambient mass spectrometry techniques. To demonstrate its applicability, metal scavengers siderophores were imaged directly from agar culture of S. wadayamensis, and well resolved and intense images were obtained using both desorption electrospray ionization (DESI) and easy ambient sonic-spray ionization (EASI) with well-defined selective spatial distributions for the free and the metal-bound molecules, providing clues for their roles in cellular metabolism. PMID:26067682

  12. Imaging Mass Spectrometry on the Nanoscale with Cluster Ion Beams

    PubMed Central

    2015-01-01

    Imaging with cluster secondary ion mass spectrometry (SIMS) is reaching a mature level of development. Using a variety of molecular ion projectiles to stimulate desorption, 3-dimensional imaging with the selectivity of mass spectrometry can now be achieved with submicrometer spatial resolution and <10 nm depth resolution. In this Perspective, stock is taken regarding what it will require to routinely achieve these remarkable properties. Issues include the chemical nature of the projectile, topography formation, differential erosion rates, and perhaps most importantly, ionization efficiency. Shortcomings of existing instrumentation are also noted. Speculation about how to successfully resolve these issues is a key part of the discussion. PMID:25458665

  13. Laser desorption mass spectrometry for DNA analysis and sequencing

    SciTech Connect

    Chen, C.H.; Taranenko, N.I.; Tang, K.; Allman, S.L.

    1995-03-01

    Laser desorption mass spectrometry has been considered as a potential new method for fast DNA sequencing. Our approach is to use matrix-assisted laser desorption to