WorldWideScience

Sample records for unit mass resolution

  1. Conflict Resolution Unit.

    Science.gov (United States)

    Busselle, Tish

    This 7-day unit, intended for use with secondary students, contains a statement of rationale and objectives, lesson plans, class assignments, teacher and student bibliographies, and suggestions for instructional materials on conflict resolution between individuals, groups, and nations. Among the six objectives listed for the unit are: 1) explain…

  2. Comparison of unit resolution SRM and TOF-MS at 12,000 mass resolution for quantitative bioanalysis of 11 steroids from human plasma.

    Science.gov (United States)

    Rousu, Timo; Tolonen, Ari

    2012-03-01

    The use of high-resolution MS systems for quantitative bioanalysis is a growing field, even though a clear majority of bioanalytical methods are still based on MS/MS with triple quadrupole (QqQ) instrumentation. The recent advances in TOF-MS technology have provided increased linear range and a high selectivity of detection by increased mass resolution and mass accuracy, making these instruments attractive for quantitative analysis due to lack of a need for compound-specific detection reaction optimization and their capability to collect data for a high number of compounds by sensitive wide mass range data acquisition. Here, 11 steroids spiked to human plasma were analyzed by LC-MS using both a QqQ MS system and a TOF instrument operating at 12,000 mass resolution. Sample preparation was performed by hybrid SPE technology. The LOD were 0.5-5 and 0.5-20 ng/ml in plasma for all analytes with QqQ and TOF-MS detection, respectively. Although the results show wider linear range and slightly better sensitivity for most of the compounds with QqQ in comparison to TOF, acceptable performance was obtained for most of the compounds within the range of LOD to 2000 ng/ml (in plasma), this was also the case with LC-TOF-MS analysis. The main problem in TOF-MS analysis at 12,000 mass resolution from plasma was selectivity rather than sensitivity or linear range.

  3. Fragmentation and Dijet Mass Resolution

    CERN Document Server

    Green, D

    2004-01-01

    At the LHC the overlap of minimum bias events and the jet energy deposits in a calorimeter causes a degradation in the dijet mass resolution. Guided by QCD, a judicious set of cuts can be developed to mitigate this degradation.

  4. High-Resolution Mass Spectrometers

    Science.gov (United States)

    Marshall, Alan G.; Hendrickson, Christopher L.

    2008-07-01

    Over the past decade, mass spectrometry has been revolutionized by access to instruments of increasingly high mass-resolving power. For small molecules up to ˜400 Da (e.g., drugs, metabolites, and various natural organic mixtures ranging from foods to petroleum), it is possible to determine elemental compositions (CcHhNnOoSsPp…) of thousands of chemical components simultaneously from accurate mass measurements (the same can be done up to 1000 Da if additional information is included). At higher mass, it becomes possible to identify proteins (including posttranslational modifications) from proteolytic peptides, as well as lipids, glycoconjugates, and other biological components. At even higher mass (˜100,000 Da or higher), it is possible to characterize posttranslational modifications of intact proteins and to map the binding surfaces of large biomolecule complexes. Here we review the principles and techniques of the highest-resolution analytical mass spectrometers (time-of-flight and Fourier transform ion cyclotron resonance and orbitrap mass analyzers) and describe some representative high-resolution applications.

  5. Determination of 2,3,7,8-chlorine-substituted dibenzo-p-dioxins and -furans at the part per trillion level in United States beef fat using high-resolution gas chromatography/high-resolution mass spectrometry

    Science.gov (United States)

    Ferrario, J.; Byrne, C.; McDaniel, D.; Dupuy, A. Jr; Harless, R.

    1996-01-01

    As part of the U.S. EPA Dioxin Reassessment Program, the 2,3,7,8-chlorine-substituted dibenzo-p-dioxins and furans were measured at part per trillion (ppt) levels in beef fat collected from slaughter facilities in the United States. This is the first statistically designed national survey of these compounds in the U.S. beef supply. Analyte concentrations were determined by high-resolution gas chromatography/high-resolution mass spectrometry, using isotope dilution methodology. Method limits of detection on a whole weight basis were 0.05 ppt for TCDD and 0.10 ppt for TCDF, 0.50 ppt for the pentas (PeCDDs/PeCDFs)/hexas (HxCDDs/HxCDFs)/heptas (HpCDDs/HpCDFs), and 3.00 ppt for the octas (OCDD/OCDF). Method detection and quantitation limits were established on the basis of demonstrated performance criteria utilizing fortified samples rather than by conventional signal-to-noise or variability of response methods. The background subtraction procedures developed for this study minimized the likelihood of false positives and increased the confidence associated with reported values near the detection limits. Mean and median values for each of the 2,3,7,8-Cl-substituted dioxins and furans are reported, along with the supporting information required for their interpretation. The mean toxic equivalence values for the samples are 0.35 ppt (nondetects = 0) and 0.89 ppt (nondetects = 1/2 LOD).

  6. High Resolution Mass Spectrometry of Polyfluorinated Polyether-Based Formulation

    Science.gov (United States)

    Dimzon, Ian Ken; Trier, Xenia; Frömel, Tobias; Helmus, Rick; Knepper, Thomas P.; de Voogt, Pim

    2016-02-01

    High resolution mass spectrometry (HRMS) was successfully applied to elucidate the structure of a polyfluorinated polyether (PFPE)-based formulation. The mass spectrum generated from direct injection into the MS was examined by identifying the different repeating units manually and with the aid of an instrument data processor. Highly accurate mass spectral data enabled the calculation of higher-order mass defects. The different plots of MW and the nth-order mass defects (up to n = 3) could aid in assessing the structure of the different repeating units and estimating their absolute and relative number per molecule. The three major repeating units were -C2H4O-, -C2F4O-, and -CF2O-. Tandem MS was used to identify the end groups that appeared to be phosphates, as well as the possible distribution of the repeating units. Reversed-phase HPLC separated of the polymer molecules on the basis of number of nonpolar repeating units. The elucidated structure resembles the structure in the published manufacturer technical data. This analytical approach to the characterization of a PFPE-based formulation can serve as a guide in analyzing not just other PFPE-based formulations but also other fluorinated and non-fluorinated polymers. The information from MS is essential in studying the physico-chemical properties of PFPEs and can help in assessing the risks they pose to the environment and to human health.

  7. SPIRAL2/DESIR high resolution mass separator

    Energy Technology Data Exchange (ETDEWEB)

    Kurtukian-Nieto, T., E-mail: kurtukia@cenbg.in2p3.fr [Centre d’Études Nucléaires de Bordeaux Gradignan, Université Bordeaux 1-CNRS/IN2P3, BP 120, F-33175 Gradignan Cedex (France); Baartman, R. [TRIUMF, 4004 Wesbrook Mall, Vancouver B.C., V6T 2A3 (Canada); Blank, B.; Chiron, T. [Centre d’Études Nucléaires de Bordeaux Gradignan, Université Bordeaux 1-CNRS/IN2P3, BP 120, F-33175 Gradignan Cedex (France); Davids, C. [Physics Division, Argonne National Laboratory, Argonne, IL 60439 (United States); Delalee, F. [Centre d’Études Nucléaires de Bordeaux Gradignan, Université Bordeaux 1-CNRS/IN2P3, BP 120, F-33175 Gradignan Cedex (France); Duval, M. [GANIL, CEA/DSM-CNRS/IN2P3, Bd Henri Becquerel, BP 55027, F-14076 Caen Cedex 5 (France); El Abbeir, S.; Fournier, A. [Centre d’Études Nucléaires de Bordeaux Gradignan, Université Bordeaux 1-CNRS/IN2P3, BP 120, F-33175 Gradignan Cedex (France); Lunney, D. [CSNSM-IN2P3-CNRS, Université de Paris Sud, F-91405 Orsay (France); Méot, F. [BNL, Upton, Long Island, New York (United States); Serani, L. [Centre d’Études Nucléaires de Bordeaux Gradignan, Université Bordeaux 1-CNRS/IN2P3, BP 120, F-33175 Gradignan Cedex (France); Stodel, M.-H.; Varenne, F. [GANIL, CEA/DSM-CNRS/IN2P3, Bd Henri Becquerel, BP 55027, F-14076 Caen Cedex 5 (France); and others

    2013-12-15

    DESIR is the low-energy part of the SPIRAL2 ISOL facility under construction at GANIL. DESIR includes a high-resolution mass separator (HRS) with a designed resolving power m/Δm of 31,000 for a 1 π-mm-mrad beam emittance, obtained using a high-intensity beam cooling device. The proposed design consists of two 90-degree magnetic dipoles, complemented by electrostatic quadrupoles, sextupoles, and a multipole, arranged in a symmetric configuration to minimize aberrations. A detailed description of the design and results of extensive simulations are given.

  8. (r) Mass Resolution versus Chamber Resolution in ALICE Dimuon Forward Spectrometer

    Institute of Scientific and Technical Information of China (English)

    WU Tao

    2007-01-01

    The precisions and its sources of spatial resolutions of tracking chambers and mass resolutions of dimuon signals in ALICE Dimuon Forward Spectrometer are explored by tracking and reconstruction of AliRoot software. The dependences of (r) mass resolution on spatial resolution of tracking chambers are presented with and without background events through simulations.

  9. Techniques for mass resolution improvement achieved by typical plasma mass analyzers: Modeling and simulations

    Science.gov (United States)

    Nicolaou, Georgios; Yamauchi, Masatoshi; Wieser, Martin; Barabash, Stas; Fedorov, Andrei

    2016-04-01

    Mass separation and particularly distinction between atomic ions and molecular ions are essential in understanding a wide range of plasma environments, with each consisted of different species with various properties. In this study we present the optimization results of light-weight (about 2 kg) magnetic mass analyzers with high g-factor for Rosetta (Ion Composition Analyser: ICA) and for Mars Express and Venus Express (Ion Mass Analyser: IMA). For the instrument's optimization we use SIMION, a 3D ion tracing software in which we can trace particle beams of several energies and directions, passing through the instrument's units. We first reproduced ICA and IMA results, which turned out to be different from simple models for low energy (< 100 eV). We then change the mechanical structure of several units of the instrument and we quantify the new mass resolution achieved with each change. Our goal is to find the optimal instrument's structure, which will allow us to achieve a proper mass resolution to distinguish atomic nitrogen from atomic oxygen for the purposes of a future magnetospheric mission.

  10. SIEMENS ADVANCED QUANTRA FTICR MASS SPECTROMETER FOR ULTRA HIGH RESOLUTION AT LOW MASS

    Energy Technology Data Exchange (ETDEWEB)

    Spencer, W; Laura Tovo, L

    2008-07-08

    . Analysis of low concentration ions, at the ppm level, required a separate analysis using ion ejection techniques. Chemical ionization due to the formation of the MH{sup +} ion or MD{sup +} increased the complexity of the spectra compared to magnetic sector mass spectra and formation of the protonated or deuterated complex was a dynamic function of the trap ion concentration. This made quantitative measurement more of a challenge. However, the resolution of the instrument was far superior to any other mass spectrometry technique that has been applied to the analysis of the hydrogen isotopes. The piezo-electric picoliter injection device offers a new way of submitting small quantities of atmospheric pressure sample gas for analysis. The new software had many improvements over the previous version but significant flaws in the beta codes remain that make the prototype units less than ideal. The instrument is a promising new technology that experience will likely improve. Unfortunately, Siemens has concluded that the technology will not be a commercial success and has decided to stop producing this product.

  11. Boundaries of mass resolution in native mass spectrometry

    NARCIS (Netherlands)

    Lössl, Philip; Snijder, Joost; Heck, Albert J R

    2014-01-01

    Over the last two decades, native mass spectrometry (MS) has emerged as a valuable tool to study intact proteins and noncovalent protein complexes. Studied experimental systems range from small-molecule (drug)-protein interactions, to nanomachineries such as the proteasome and ribosome, to even viru

  12. Fragmentation reactions of labeled and untabeled Rhodamine B in a high-resolution Fourier transform ion cyclotron resonance mass spectrometer.

    Science.gov (United States)

    Clemen, Martin; Gernert, Claus; Peters, Jonathan; Grotemeyer, Jürgen

    2013-01-01

    The fragmentation reactions of Rhodamine B have been investigated by the use of electrospray ionization mass spectra in a high mass resolving ion cyclotron resonance mass spectrometer. Using high resolution, it could be shown that the loss of 44 mass units from the molecular ion is due to propane; the measured masses were inconsistent with loss of carbon dioxide. These conclusions are supported using deuterium-labeled Rhodamine B. This sample again only shows the loss of fully-deuterated propane verifying the high-resolution data. These findings illustrate very clearly that the conclusions based solely on low resolution spectra were false. The general implication on fragmentations of aromatic acids is discussed.

  13. INTERNET CONNECTIVITY FOR MASS PRODUCED UNITS WITHOUT USER INTERFACE

    DEFF Research Database (Denmark)

    2000-01-01

    To the manufacturer of mass produced units without a user interface, typically field level units, connection of these units to a communications network for enabling servicing, control and trackability is of interest. To provide this connection, a solution is described in which an interface...... comprising an ASIC is built into a mass produced unit, whereby the ASIC is incorporating selected portions of selected layers of the Internet Protocol. The mass produced unit is then allocated a unit address....

  14. Automated data processing of high-resolution mass spectra

    DEFF Research Database (Denmark)

    Hansen, Michael Adsetts Edberg; Smedsgaard, Jørn

    There has been an almost explosive growth in performance and applications of Electrospray Ionization (ESI) Time of Flight (TOF) mass spectrometry, which today is one of the most efficient tools for screening of metabolites in complex bio-samples. Most efficiently ESI-MS can be used by directly...... infusion of crude extracts into the source taking advantage of the high sensitivity, high mass resolution and accuracy and the limited fragmentation. Unfortunately, there has not been a comparable development in the data processing techniques to fully exploit gain in high resolution and accuracy...... and mass axis on to a fixed one-dimensional array, we obtain a vector that can be used directly as input in multivariate statistics or library search methods. We demonstrate that both cluster- and discriminant analysis as well as PCA (and related methods) can be applied directly on mass spectra from direct...

  15. Yeast expression proteomics by high-resolution mass spectrometry

    DEFF Research Database (Denmark)

    Walther, Tobias C; Olsen, Jesper Velgaard; Mann, Matthias

    2010-01-01

    -translational controls contribute majorly to regulation of protein abundance, for example in heat shock stress response. The development of new sample preparation methods, high-resolution mass spectrometry and novel bioinfomatic tools close this gap and allow the global quantitation of the yeast proteome under different...... conditions. Here, we provide background information on proteomics by mass-spectrometry and describe the practice of a comprehensive yeast proteome analysis....

  16. A new matching algorithm for high resolution mass spectra

    DEFF Research Database (Denmark)

    Hansen, Michael Edberg; Smedsgaard, Jørn

    2004-01-01

    We present a new matching algorithm designed to compare high-resolution spectra. Whereas existing methods are bound to compare fixed intervals of ion masses, the accurate mass spectrum (AMS) distance method presented here is independent of any alignment. Based on the Jeffreys-Matusitas (JM......) distance, a difference between observed peaks across pairs of spectra can be calculated, and used to find a unique correspondence between the peaks. The method takes into account that there may be differences in resolution of the spectra. The algorithm is used for indexing in a database containing 80...... accurate mass spectra from an analysis of extracts of 80 isolates representing the nine closely related species in the Penicillium series Viridicata. Using this algorithm we can obtain a retrieval performance of approximate to97-98% that is comparable with the best of the existing methods (e.g., the dot...

  17. Image resolution influence on determination of resin injection rock mass

    Science.gov (United States)

    Wang, Weixing; Hakami, Eva

    2006-01-01

    In the context of nuclear waste repositories, an important approach to understanding brittle rock mass behavior to integrate new and powerful observational and numerical methods with multi-functional 3-D imaging and visualization techniques. Since 1994, Swedish Nuclear Fuel and Waste Management Company (SKB) have identified the need for a better understanding of radionuclide transport and retention processes in fractured rock. As a cooperation project between Sweden and China, we sampled a number of rock specimens for analyze rock fracture network by optical image technique. The samples are resin injected, in which way; opened fractures can be seen clearly by means of UV (Ultraviolet) light illumination. In the study period, we used different optical focuses to obtain the images from the same samples; we found that Image resolution influences on porosity determination of resin injected rock mass. This paper presents and discusses the six issues based on our research results: (1) Fracture porosity increases as camera focus distance decreases; (2) Porosity increases as illumination increases in resin injected fracture images; (3) To roughly estimate the porosity, the low resolution image can be used; (4) To collect more details of fracture information, the high resolution image is needed; (5) The resolution of image should be determined based on the aim of fracture analysis; (6) To acquire high resolution image, constructing a special illumination (standard) box maybe helpful to avoid light reflection and diffusion.

  18. A high-resolution record of Greenland mass balance

    Science.gov (United States)

    McMillan, Malcolm; Leeson, Amber; Shepherd, Andrew; Briggs, Kate; Armitage, Thomas W. K.; Hogg, Anna; Kuipers Munneke, Peter; Broeke, Michiel; Noël, Brice; Berg, Willem Jan; Ligtenberg, Stefan; Horwath, Martin; Groh, Andreas; Muir, Alan; Gilbert, Lin

    2016-07-01

    We map recent Greenland Ice Sheet elevation change at high spatial (5 km) and temporal (monthly) resolution using CryoSat-2 altimetry. After correcting for the impact of changing snowpack properties associated with unprecedented surface melting in 2012, we find good agreement (3 cm/yr bias) with airborne measurements. With the aid of regional climate and firn modeling, we compute high spatial and temporal resolution records of Greenland mass evolution, which correlate (R = 0.96) with monthly satellite gravimetry and reveal glacier dynamic imbalance. During 2011-2014, Greenland mass loss averaged 269 ± 51 Gt/yr. Atmospherically driven losses were widespread, with surface melt variability driving large fluctuations in the annual mass deficit. Terminus regions of five dynamically thinning glaciers, which constitute less than 1% of Greenland's area, contributed more than 12% of the net ice loss. This high-resolution record demonstrates that mass deficits extending over small spatial and temporal scales have made a relatively large contribution to recent ice sheet imbalance.

  19. High Resolution Studies of Mass Loss from Massive Binary Stars

    Science.gov (United States)

    Corcoran, Michael F.; Gull, Theodore R.; Hamaguchi, Kenji; Richardson, Noel; Madura, Thomas; Post Russell, Christopher Michael; Teodoro, Mairan; Nichols, Joy S.; Moffat, Anthony F. J.; Shenar, Tomer; Pablo, Herbert

    2017-01-01

    Mass loss from hot luminous single and binary stars has a significant, perhaps decisive, effect on their evolution. The combination of X-ray observations of hot shocked gas embedded in the stellar winds and high-resolution optical/UV spectra of the cooler mass in the outflow provides unique ways to study the unstable process by which massive stars lose mass both through continuous stellar winds and rare, impulsive, large-scale mass ejections. The ability to obtain coordinated observations with the Hubble Space Telescope Imaging Spectrograph (HST/STIS) and the Chandra High-Energy Transmission Grating Spectrometer (HETGS) and other X-ray observatories has allowed, for the first time, studies of resolved line emisssion over the temperature range of 104- 108K, and has provided observations to confront numerical dynamical models in three dimensions. Such observations advance our knowledge of mass-loss asymmetries, spatial and temporal variabilities, and the fundamental underlying physics of the hot shocked outflow, providing more realistic constraints on the amount of mass lost by different luminous stars in a variety of evolutionary stages. We discuss the impact that these joint observational studies have had on our understanding of dynamical mass outflows from massive stars, with particular emphasis on two important massive binaries, Delta Ori Aa, a linchpin of the mass luminosity relation for upper HRD main sequence stars, and the supermassive colliding wind binary Eta Carinae.

  20. Intact MicroRNA Analysis Using High Resolution Mass Spectrometry

    Science.gov (United States)

    Kullolli, Majlinda; Knouf, Emily; Arampatzidou, Maria; Tewari, Muneesh; Pitteri, Sharon J.

    2014-01-01

    MicroRNAs (miRNAs) are small single-stranded non-coding RNAs that post-transcriptionally regulate gene expression, and play key roles in the regulation of a variety of cellular processes and in disease. New tools to analyze miRNAs will add understanding of the physiological origins and biological functions of this class of molecules. In this study, we investigate the utility of high resolution mass spectrometry for the analysis of miRNAs through proof-of-concept experiments. We demonstrate the ability of mass spectrometry to resolve and separate miRNAs and corresponding 3' variants in mixtures. The mass accuracy of the monoisotopic deprotonated peaks from various miRNAs is in the low ppm range. We compare fragmentation of miRNA by collision-induced dissociation (CID) and by higher-energy collisional dissociation (HCD) which yields similar sequence coverage from both methods but additional fragmentation by HCD versus CID. We measure the linear dynamic range, limit of detection, and limit of quantitation of miRNA loaded onto a C18 column. Lastly, we explore the use of data-dependent acquisition of MS/MS spectra of miRNA during online LC-MS and demonstrate that multiple charge states can be fragmented, yielding nearly full sequence coverage of miRNA on a chromatographic time scale. We conclude that high resolution mass spectrometry allows the separation and measurement of miRNAs in mixtures and a standard LC-MS setup can be adapted for online analysis of these molecules.

  1. Novel negative mass density resonant metamaterial unit cell

    Energy Technology Data Exchange (ETDEWEB)

    Cselyuszka, Norbert, E-mail: cselyu@yahoo.com; Sečujski, Milan, E-mail: secujski@uns.ac.rs; Crnojević-Bengin, Vesna, E-mail: bengin@uns.ac.rs

    2015-01-02

    In this paper a novel resonant unit cell of one-dimensional acoustic metamaterials is presented, which exhibits negative effective mass density. We theoretically analyze the unit cell and develop a closed analytical formula for its effective mass density. Then we proceed to demonstrate left-handed propagation of acoustic waves using the proposed unit cell. Finally, we present its dual-band version, capable of operating at two independent frequencies. - Highlights: • A novel acoustic metamaterial unit cell provides Lorentz-type resonant effective mass density. • Analytical formula for effective mass density is derived. • Acoustic bandstop medium and left-handed metamaterial based on the novel unit cell are presented. • Modified version of the unit cell, operating at two independent frequencies, is proposed.

  2. Five Micron High Resolution MALDI Mass Spectrometry Imaging with Simple, Interchangeable, Multi-Resolution Optical System

    Science.gov (United States)

    Feenstra, Adam D.; Dueñas, Maria Emilia; Lee, Young Jin

    2017-01-01

    High-spatial resolution mass spectrometry imaging (MSI) is crucial for the mapping of chemical distributions at the cellular and subcellular level. In this work, we improved our previous laser optical system for matrix-assisted laser desorption ionization (MALDI)-MSI, from 9 μm practical laser spot size to a practical laser spot size of 4 μm, thereby allowing for 5 μm resolution imaging without oversampling. This is accomplished through a combination of spatial filtering, beam expansion, and reduction of the final focal length. Most importantly, the new laser optics system allows for simple modification of the spot size solely through the interchanging of the beam expander component. Using 10×, 5×, and no beam expander, we could routinely change between 4, 7, and 45 μm laser spot size, in less than 5 min. We applied this multi-resolution MALDI-MSI system to a single maize root tissue section with three different spatial resolutions of 5, 10, and 50 μm and compared the differences in imaging quality and signal sensitivity. We also demonstrated the difference in depth of focus between the optical systems with 10× and 5× beam expanders.

  3. High resolution weak lensing mass mapping combining shear and flexion

    Science.gov (United States)

    Lanusse, F.; Starck, J.-L.; Leonard, A.; Pires, S.

    2016-06-01

    Aims: We propose a new mass mapping algorithm, specifically designed to recover small-scale information from a combination of gravitational shear and flexion. Including flexion allows us to supplement the shear on small scales in order to increase the sensitivity to substructures and the overall resolution of the convergence map without relying on strong lensing constraints. Methods: To preserve all available small scale information, we avoid any binning of the irregularly sampled input shear and flexion fields and treat the mass mapping problem as a general ill-posed inverse problem, which is regularised using a robust multi-scale wavelet sparsity prior. The resulting algorithm incorporates redshift, reduced shear, and reduced flexion measurements for individual galaxies and is made highly efficient by the use of fast Fourier estimators. Results: We tested our reconstruction method on a set of realistic weak lensing simulations corresponding to typical HST/ACS cluster observations and demonstrate our ability to recover substructures with the inclusion of flexion, which are otherwise lost if only shear information is used. In particular, we can detect substructures on the 15'' scale well outside of the critical region of the clusters. In addition, flexion also helps to constrain the shape of the central regions of the main dark matter halos. Our mass mapping software, called Glimpse2D, is made freely available at http://www.cosmostat.org/software/glimpse

  4. Quantitative proteomics using the high resolution accurate mass capabilities of the quadrupole-orbitrap mass spectrometer.

    Science.gov (United States)

    Gallien, Sebastien; Domon, Bruno

    2014-08-01

    High resolution/accurate mass hybrid mass spectrometers have considerably advanced shotgun proteomics and the recent introduction of fast sequencing capabilities has expanded its use for targeted approaches. More specifically, the quadrupole-orbitrap instrument has a unique configuration and its new features enable a wide range of experiments. An overview of the analytical capabilities of this instrument is presented, with a focus on its application to quantitative analyses. The high resolution, the trapping capability and the versatility of the instrument have allowed quantitative proteomic workflows to be redefined and new data acquisition schemes to be developed. The initial proteomic applications have shown an improvement of the analytical performance. However, as quantification relies on ion trapping, instead of ion beam, further refinement of the technique can be expected.

  5. HCN Polymers: Toward Structure Comprehension Using High Resolution Mass Spectrometry

    Science.gov (United States)

    Bonnet, Jean-Yves; Thissen, Roland; Frisari, Ma; Vuitton, Veronique; Quirico, Eric; Le Roy, Léna; Fray, Nicolas; Cottin, Hervé; Horst, Sarah; Yelle, Roger

    A lot of solar system materials, including cometary ices and Titan aerosols, contain dark matter that can be interpreted as complex nitrogen bearing organic matter [1]. In laboratory experi-ments, HCN polymers are thus analogs of great interest. In fact they may be present in Titan atmosphere and in comet nuclei and then reprocessed as a CN distributed source [2], when ices began to sublimate and ejects from the nucleus organic matter grains [3]. The presence of HCN polymers is suggested because HCN molecule has been directly observed in 1P/Halley comet [4] and others. HCN polymers are also of prebiotic interest [5] as it can form amino acid under hydrolysis conditions. Even if they have been studied during the last decades, their chemical composition and structure are still poorly understood, and a great analytical effort has to be continued. In this way we present a high resolution mass spectrometry (HRMS) and a high resolution tandem mass spectrometry (MS/HRMS) analysis of HCN polymers. It was shown [6] that this is a suitable technique to elucidate composition and structure of the soluble part of tholins analogs of Titan's atmosphere aerosols. HCN polymers have never been studied by HRMS, thus we used a LTQ-Orbitrap XL high resolution mass spectrometer to analyse the HCN polymers. These are produced at LISA by direct polymerisation of pure liquid HCN, catalyzed by ammonia. HCN polymers have been completely dissolved in methanol and then injected in the mass spectrometer by ElectroSpray Ionization (ESI). This atmospheric pressure ionization process produces protonated or deprotonated ions, but it does not fragment molecules. Thus HRMS, allows a direct access to the stoechiometry of all the ionizable molecules present in the samples. Fragmentation analyses (MS/MS) of selected ions have also been performed. Thess analysis provide information about the different chemical fonctionnalities present in HCN poly-mers and also about their structure. Thus we are able to

  6. Proteogenomic analysis of Mycobacterium smegmatis using high resolution mass spectrometry

    Directory of Open Access Journals (Sweden)

    Matthys Gerhardus Potgieter

    2016-04-01

    Full Text Available AbstractBiochemical evidence is vital for accurate genome annotation. The integration of experimental data collected at the proteome level using high resolution mass spectrometry allows for improvements in genome annotation by providing evidence for novel gene models, while validating or modifying others. Here we report the results of a proteogenomic analysis of a reference strain of Mycobacterium smegmatis (mc2155, a fast growing model organism for the pathogenic Mycobacterium tuberculosis - the causative agent for Tuberculosis. By integrating high throughput LC/MS/MS proteomic data with genomic six frame translation and ab initio gene prediction databases, a total of 2887 ORFs were identified, including 2810 ORFs annotated to a Reference protein, and 63 ORFs not previously annotated to a Reference protein. Further, the translational start site (TSS was validated for 558 Reference proteome gene models, while upstream translational evidence was identified for 81. In addition, N-terminus derived peptide identifications allowed for downstream TSS modification of a further 24 gene models. We validated the existence of 6 previously described interrupted coding sequences at the peptide level, and provide evidence for 4 novel frameshift positions. Analysis of peptide posterior error probability (PEP scores indicates high-confidence novel peptide identifications and shows that the genome of M. smegmatis mc2155 is not yet fully annotated. Data are available via ProteomeXchange with identifier PXD003500.

  7. High mass resolution time of flight mass spectrometer for measuring products in heterogeneous catalysis in highly sensitive microreactors

    DEFF Research Database (Denmark)

    Andersen, Thomas; Jensen, Robert; Christensen, M. K.

    2012-01-01

    response. Gas analysis is performed with a time of flight mass spectrometer with a modified nude Bayard-Alpert ionization gauge as gas ionization source. The mass resolution of the time of flight mass spectrometer using the ion gauge as ionization source is estimated to m∕Δm > 2500. The system design...

  8. 100-Meter Resolution Satellite View of the Conterminous United States - Direct Download

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — The Satellite View of the Conterminous United States map layer is a 100-meter resolution simulated natural-color image of the United States. Vegetation is generally...

  9. 100-Meter Resolution Satellite View with Shaded Relief of the Conterminous United States - Direct Download

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — The Satellite View with Shaded Relief of the Conterminous United States map layer is a 100-meter resolution simulated natural-color image of the United States, with...

  10. 100-Meter Resolution Color Shaded Relief of the Conterminous United States - Direct Download

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — The Color Shaded Relief of the Conterminous United States map layer is a 100-meter resolution color-sliced elevation image of the United States, with relief shading...

  11. 100-Meter Resolution Land/Water Mask of the Conterminous United States - Direct Download

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — This Land/Water Mask is a 100-meter resolution image of the conterminous United States, with separate values for oceans and for land areas of the United States,...

  12. 100-Meter Resolution Color-Sliced Elevation of the Conterminous United States - Direct Download

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — The map layer of Color-Sliced Elevation of the Conterminous United States is a 100-meter resolution elevation image of the United States, in an Albers Equal-Area...

  13. 100-Meter Resolution Grayscale Shaded Relief of the Conterminous United States - Direct Download

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — The Grayscale Shaded Relief of the Conterminous United States map layer is a 100-meter resolution grayscale shaded relief image of the United States, in an Albers...

  14. Quantitation of Acrylamide in Foods by High-Resolution Mass Spectrometry

    NARCIS (Netherlands)

    Troise, A.D.; Fogliano, Vincenzo

    2016-01-01

    The use of liquid chromatography high-resolution mass spectrometry (LC-HRMS) and direct analysis real-time high-resolution mass spectrometry (DART-HRMS) defines a new scenario in the analysis of thermal-induced toxicants, such as acrylamide. Several factors contribute to the definition of the

  15. Quantitation of Acrylamide in Foods by High-Resolution Mass Spectrometry

    NARCIS (Netherlands)

    Troise, A.D.; Fogliano, Vincenzo

    2016-01-01

    The use of liquid chromatography high-resolution mass spectrometry (LC-HRMS) and direct analysis real-time high-resolution mass spectrometry (DART-HRMS) defines a new scenario in the analysis of thermal-induced toxicants, such as acrylamide. Several factors contribute to the definition of the com

  16. Quantifying Stellar Mass Loss with High Angular Resolution Imaging

    CERN Document Server

    Ridgway, Stephen; Creech-Eakman, Michelle; Elias, Nicholas; Howell, Steve; Hutter, Don; Karovska, Margarita; Ragland, Sam; Wishnow, Ed; Zhao, Ming

    2009-01-01

    Mass is constantly being recycled in the universe. One of the most powerful recycling paths is via stellar mass-loss. All stars exhibit mass loss with rates ranging from ~10(-14) to 10(-4) M(sun) yr-1, depending on spectral type, luminosity class, rotation rate, companion proximity, and evolutionary stage. The first generation of stars consisted mostly of hydrogen and helium. These shed material - via massive winds, planetary nebulae and supernova explosions - seeding the interstellar medium with heavier elements. Subsequent generations of stars incorporated this material, changing how stars burn and providing material for planet formation. An understanding of mass loss is critical for modeling individual stars as well as answering larger astrophysical questions. Understanding mass loss is essential for following the evolution of single stars, binaries, star clusters, and galaxies. Mass loss is one of our weakest areas in the modeling of fundamental stellar processes. In large part this is owing to lack of co...

  17. Disseminating the unit of mass from multiple primary realisations

    Science.gov (United States)

    Nielsen, Lars

    2016-12-01

    When a new definition of the kilogram has been adopted in 2018 as expected, the unit of mass will be realised by the watt balance method, the x-ray crystal density method or perhaps other primary methods still to be developed. So far, the standard uncertainties associated with the available primary methods are at least one order of magnitude larger than the standard uncertainty associated with mass comparisons using mass comparators, so differences in primary realisations of the kilogram are easily detected, whereas many National Metrology Institutes would have to increase their calibration and measurement capabilities (CMCs) if they were traceable to a single primary realisation. This paper presents a scheme for obtaining traceability to multiple primary realisations of the kilogram using a small group of stainless steel 1 kg weights, which are allowed to change their masses over time in a way known to be realistic, and which are calibrated and stored in air. An analysis of the scheme shows that if the relative standard uncertainties of future primary realisations are equal to the relative standard uncertainties of the present methods used to measure the Planck constant, the unit of mass can be disseminated with a standard uncertainty less than 0.015 mg, which matches the smallest CMCs currently claimed for the calibration of 1 kg weights.

  18. Identification of novel metabolites from Aspergillus flavus by high resolution and multiple stage mass spectrometry.

    Science.gov (United States)

    Malysheva, Svetlana V; Arroyo-Manzanares, Natalia; Cary, Jeffrey W; Ehrlich, Kenneth C; Vanden Bussche, Julie; Vanhaecke, Lynn; Bhatnagar, Deepak; Di Mavungu, José Diana; De Saeger, Sarah

    2014-01-01

    The filamentous fungus Aspergillus flavus is one of the most important species in the Aspergillus genus and is distributed worldwide as a prevalent aflatoxin-producing food and feed contaminant. A. flavus contains more than 55 gene clusters that are predicted to encode proteins involved in secondary metabolite production. One of these, cluster 27, contains a polyketide synthase (pks27) gene that encodes a protein that is highly homologous to the aflatoxin cluster PKS. Comparative metabolomics, using ultra-high performance liquid chromatography (UHPLC) coupled to high resolution Orbitrap mass spectrometry (MS) was used to detect metabolites differentially expressed in the A. flavus wild-type and ∆pks27 mutant strains. Metabolite profiling was aided by a statistical differential analysis of MS data using SIEVE software. This differential analysis combined with accurate mass data from the Orbitrap and ion trap multiple stage MS allowed four metabolites to be identified that were produced only by the wild-type culture. These included asparasone A (358 Da), an anthraquinone pigment, and related anthraquinones with masses of 316, 340 and 374 Da. These latter three compounds had similar fragmentation patterns to that of asparasone A. The 316 Da anthraquinone is particularly interesting because it is most likely formed by incorporation of seven malonyl-CoA units rather than the eight units required for the formation of asparasone A. The 340 and 374 Da metabolites are the dehydration and an oxy-derivative of asparasone A, respectively. Asparasone A was also identified in extracts from several other Aspergillus species.

  19. A fragmentation study of kaempferol using electrospray quadrupole time-of-flight mass spectrometry at high mass resolution

    Science.gov (United States)

    March, Raymond E.; Miao, Xiu-Sheng

    2004-02-01

    A mass spectrometric method based on the combined use of electrospray ionization, collision-induced dissociation and tandem mass spectrometry at high mass resolution has been applied to an investigation of the structural characterization of protonated and deprotonated kaempferol (3,5,7,4'-tetrahydroxyflavone). Low-energy product ion mass spectra of [M+H]+ ions showed simple fragmentations of the C ring that permitted characterization of the substituents in the A and B rings. In addition, four rearrangement reactions accompanied by losses of C2H2O, CHO[radical sign], CO, and H2O were observed. Low-energy product ion mass spectra of [M-H]- ions showed only four rearrangement reactions accompanied by losses of OH[radical sign], CO, CH2O, and C2H2O. The use of elevated cone voltages permitted observation of product ion mass spectra of selected primary and secondary fragment ions so that each fragment ion reported was observed as a direct product of its immediate precursor ion. Product ion mass spectra examined at high mass resolution allowed unambiguous determination of the elemental composition of fragment ions and resolution of two pairs of isobars. Fragmentation mechanisms and ion structures have been proposed.

  20. Implications of United Nations Security Council Resolutions 1970

    Directory of Open Access Journals (Sweden)

    JOHANNES VAN AGGELEN

    2011-11-01

    Full Text Available The article shows the increasing legislative power of the UN Security Council over the last two decades, although the doctrine is not unanimous on the issue. The Council,in itstwo resolutions (1970 and 1973 took new measures,not seen in previous resolutions. Libya appeared recently before the Human Rights Council and the report,very good in the eyes of the government,was seriously critized.The events as of february and the government’s reaction defies the content of the report. Libya committed flagrant violations of human rights.The Human Rights Council established a group of experts,which in early June published a detailed report which testified to grave violations.

  1. USGS 100-Meter Resolution Land Cover of the Conterminous United States 201501 TIFF

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — This map layer contains land cover data for the conterminous United States, in an Albers Equal-Area Conic projection and at a resolution of 100 meters. The land...

  2. 100-Meter Resolution Tree Canopy of the Conterminous United States - Direct Download

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — This map layer contains tree canopy data for the conterminous United States, in an Albers Equal-Area Conic projection and at a resolution of 100 meters. The tree...

  3. 100-Meter Resolution Land Cover of the Conterminous United States - Direct Download

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — This map layer contains land cover data for the conterminous United States, in an Albers Equal-Area Conic projection and at a resolution of 100 meters. The land...

  4. 100-Meter Resolution Impervious Surface of the Conterminous United States - Direct Download

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — This map layer contains impervious surface data for the conterminous United States, in an Albers Equal-Area Conic projection and at a resolution of 100 meters. The...

  5. A new, high-resolution global mass coral bleaching database.

    Science.gov (United States)

    Donner, Simon D; Rickbeil, Gregory J M; Heron, Scott F

    2017-01-01

    Episodes of mass coral bleaching have been reported in recent decades and have raised concerns about the future of coral reefs on a warming planet. Despite the efforts to enhance and coordinate coral reef monitoring within and across countries, our knowledge of the geographic extent of mass coral bleaching over the past few decades is incomplete. Existing databases, like ReefBase, are limited by the voluntary nature of contributions, geographical biases in data collection, and the variations in the spatial scale of bleaching reports. In this study, we have developed the first-ever gridded, global-scale historical coral bleaching database. First, we conducted a targeted search for bleaching reports not included in ReefBase by personally contacting scientists and divers conducting monitoring in under-reported locations and by extracting data from the literature. This search increased the number of observed bleaching reports by 79%, from 4146 to 7429. Second, we employed spatial interpolation techniques to develop annual 0.04° × 0.04° latitude-longitude global maps of the probability that bleaching occurred for 1985 through 2010. Initial results indicate that the area of coral reefs with a more likely than not (>50%) or likely (>66%) probability of bleaching was eight times higher in the second half of the assessed time period, after the 1997/1998 El Niño. The results also indicate that annual maximum Degree Heating Weeks, a measure of thermal stress, for coral reefs with a high probability of bleaching increased over time. The database will help the scientific community more accurately assess the change in the frequency of mass coral bleaching events, validate methods of predicting mass coral bleaching, and test whether coral reefs are adjusting to rising ocean temperatures.

  6. Coherent optical propagation and ultrahigh resolution mass sensor based on photonic molecules optomechanics

    Science.gov (United States)

    Chen, Hua-Jun; Chen, Chang-Zhao; Li, Yang; Fang, Xian-Wen; Tang, Xu-Dong

    2017-01-01

    We theoretically demonstrate the coherent optical propagation properties based on a photonic molecules optomechanics. With choosing a suitable detuning of the pump field from optomechanical cavity resonance, both the slow- and fast-light effect of the probe field appear in the system. The coupling strength of the two cavities play a key role, which affords a quantum channel and influences the width of the transparency window. Based on the photonic molecules optomechanical system, a high resolution mass sensor is also proposed. The mass of external nanoparticles deposited onto the cavity can be measured straightforward via tracking the mechanical resonance frequency shifts due to mass changes in the probe transmission spectrum. Compared with the single-cavity optomechanics mass sensors, the mass resolution is improved significantly due to the cavity-cavity coupling. The photonic molecules optomechanics provide a new platform for on-chip applications in quantum information processing and ultrahigh resolution sensor devices.

  7. A High Resolution Orbitrap Mass Spectrometer for In-Situ Analysis in Planetary Science

    Science.gov (United States)

    Briois, C.; Thirkell, L.; Boukrara, A.; Lebreton, J. P.; Thissen, R.; Puget, P.; Cottin, H.; Grand, N.; Pennanech, C.; Zapf, P.; Szopa, C.; Carrasco, N.; Chapuis, C.; Bouabdellah, A.; Berthelier, J. J.; Engrand, C.; Makarov, A.

    2012-04-01

    Solar System exploration is dealing more and more with chemically complex matter, potentially associated with astrobiology or prebiotic questions, requiring optimized methods of analysis. Due to its ability to reveal quantitatively almost any chemical element, mass spectrometry has served as an invaluable scientific analytical instruments. Nevertheless the best mass resolution (M/deltaM) currently achieved by mass spectrometers in space is about 3000 at mass 28 (ROSINA's DFMS on board ESA's comet chaser Rosetta). This resolution allows separation of peaks for only a limited number of isobaric species (e.g. N2 / CO at 28 Da). Yet, purely electrostatic orbital traps in laboratory are showing mass resolution above 100 000 for m/z <= 400 [1, 2], that provides separation for each detected isobaric species. Therefore it opens new opportunity for molecular characterization, isotopic abundance evaluation, and more generally environmental characterization. Our French consortium of laboratories, in collaboration with ThermoFischer Scientific, is currently working on the adaptation of this type of mass spectrometer for space instrumentation. We present here this innovative concept of mass analyzer for space that is lightweight, uses DC voltages, and provides ultra high resolving power capabilities. A mass resolution of 140,000 at mass 56 has been recently achieved with our prototype.

  8. A New Method for Characterizing Very-Low-Mass Companions with Low Resolution Near-Infrared Spectroscopy

    CERN Document Server

    Rice, Emily L; Zimmerman, Neil; Roberts, Lewis C; Hinkley, Sasha

    2015-01-01

    We present a new and computationally efficient method for characterizing very low mass companions using low resolution ($R\\sim$30) near-infrared ($YJH$) spectra from high contrast imaging campaigns with integral field spectrograph (IFS) units. We conduct a detailed quantitative comparison of the efficacy of this method through tests on simulated data comparable in spectral coverage and resolution to the currently operating direct imaging systems around the world. In particular, we simulate Project 1640 data as an example of the use, accuracy, and precision of this technique. We present results from comparing simulated spectra of M, L, and T dwarfs with a large and finely-sampled grid of synthetic spectra using Markov Chain Monte Carlo techniques. We determine the precision and accuracy of effective temperature and surface gravity inferred from fits to PHOENIX dusty and cond, which we find reproduce the low-resolution spectra of all objects within the adopted flux uncertainties. Uncertainties in effective temp...

  9. High Resolution Mass Spectrometry of Polyfluorinated Polyether-Based Formulation

    DEFF Research Database (Denmark)

    Dimzon, Ian Ken; Trier, Xenia; Frömel, Tobias

    2016-01-01

    of nonpolar repeating units. The elucidated structure resembles the structure in the published manufacturer technical data. This analytical approach to the characterization of a PFPE-based formulation can serve as a guide in analyzing not just other PFPE-based formulations but also other fluorinated and non......-fluorinated polymers. The information from MS is essential in studying the physico-chemical properties of PFPEs and can help in assessing the risks they pose to the environment and to human health. Graphical Abstract ᅟ....

  10. High resolution ultrasound characterization of soft tissue masses in children. [Comparison with CT findings

    Energy Technology Data Exchange (ETDEWEB)

    Glasier, C.M.; Seibert, J.J.; Williamson, S.L.; Seibert, R.W.; Lange, T.A.; Corbitt, S.L.; Rodgers, A.B.

    1987-03-01

    Forty-two soft tissue masses in infants and children were examined with high resolution ultrasonography. Sonography was diagnostically specific in 17/42 (40%), useful but not diagnostic in 24/42 (58%), and misleading in 1/42 (2%) of soft tissue masses. Lesions with diagnostic sonographic features included cystic hygroma, fibromatosis colli, lymphadenopathy with abscess formation, and one case of osteomyelitis.

  11. High-resolution Fourier transform ion cyclotron resonance mass spectrometry with increased throughput for biomolecular analysis.

    Science.gov (United States)

    Nagornov, Konstantin O; Gorshkov, Mikhail V; Kozhinov, Anton N; Tsybin, Yury O

    2014-09-16

    A multielectrode ion cyclotron resonance (ICR) cell, herein referred to as the "4X cell", for signal detection at the quadruple frequency multiple was implemented and characterized on a commercial 10 T Fourier transform ICR mass spectrometer (FT-ICR MS). Notably, with the 4X cell operating at a 10 T magnetic field we achieved a 4-fold increase in MS acquisition rate per unit of resolving power for signal detection periods typically employed in FTMS, viz., shorter than 6 s. Effectively, the obtained resolution performance represents the limit of the standard measurement principle with dipolar signal detection and FT signal processing at an equivalent magnetic field of 40 T. In other words, the achieved resolving powers are 4 times higher than those provided by 10 T FT-ICR MS with a standard ICR cell. For example, resolving powers of 170,000 and 70,000 were obtained in magnitude-mode Fourier spectra of 768 and 192 ms apodized transient signals acquired for a singly charged fluorinated phosphazine (m/z 1422) and a 19-fold charged myoglobin (MW 16.9 kDa), respectively. In peptide analysis, the baseline-resolved isotopic fine structures were obtained with as short as 768 ms transients. In intact protein analysis, the average resolving power of 340,000 across the baseline-resolved (13)C isotopic pattern of multiply charged ions of bovine serum albumin was obtained with 1.5 s transients. The dynamic range and the mass measurement accuracy of the 4X cell were found to be comparable to the ones obtained for the standard ICR cell on the same mass spectrometer. Overall, the reported results validate the advantages of signal detection at frequency multiples for increased throughput in FT-ICR MS, essential for numerous applications with time constraints, including proteomics.

  12. Mass defect filter technique and its applications to drug metabolite identification by high-resolution mass spectrometry.

    Science.gov (United States)

    Zhang, Haiying; Zhang, Donglu; Ray, Kenneth; Zhu, Mingshe

    2009-07-01

    Identification of drug metabolites by liquid chromatography/mass spectrometry (LC/MS) involves metabolite detection in biological matrixes and structural characterization based on product ion spectra. Traditionally, metabolite detection is accomplished primarily on the basis of predicted molecular masses or fragmentation patterns of metabolites using triple-quadrupole and ion trap mass spectrometers. Recently, a novel mass defect filter (MDF) technique has been developed, which enables high-resolution mass spectrometers to be utilized for detecting both predicted and unexpected drug metabolites based on narrow, well-defined mass defect ranges for these metabolites. This is a new approach that is completely different from, but complementary to, traditional molecular mass- or MS/MS fragmentation-based LC/MS approaches. This article reviews the mass defect patterns of various classes of drug metabolites and the basic principles of the MDF approach. Examples are given on the applications of the MDF technique to the detection of stable and chemically reactive metabolites in vitro and in vivo. Advantages, limitations, and future applications are also discussed on MDF and its combinations with other data mining techniques for the detection and identification of drug metabolites.

  13. Resolving mass flux at high spatial and temporal resolution using GRACE intersatellite measurements

    DEFF Research Database (Denmark)

    Rowlands, D. D.; Luthcke, S. B.; Klosko, S. M.

    2005-01-01

    The GRACE mission is designed to monitor mass flux on the Earth's surface at one month and high spatial resolution through the estimation of monthly gravity fields. Although this approach has been largely successful, information at submonthly time scales can be lost or even aliased through...... resolution. Using 4° × 4° blocks at 10-day intervals, we estimate the mass of surplus or deficit water over a 52° × 60° grid centered on the Amazon basin for July 2003. We demonstrate that the recovered signals are coherent and correlate well with the expected hydrological signal....

  14. Mass Metrology and the International System of Units (SI)

    Science.gov (United States)

    Davis, Richard S.

    The International System of Units (SI) is widely used in science, industry, and commerce because it caters simultaneously to the needs of all. In the early twenty-first century, this means defining the units of time, length, mass, and electricity in terms of the fundamental constants of physics, and then "realizing" these definitions to sufficient accuracy on the human scale of the second, meter, kilogram, and ampere. This program has already been successful except for the kilogram, which is still defined in terms of an artifact constructed in the late nineteenth century. Although quantum-based electrical standards are widely used, the SI voltages or resistances produced by these standards depend on the values of constants that are at present based on experimental values derived from the artifact kilogram. This chapter presents the current state of affairs, which is unsatisfactory, and proceeds to describe work that will lead to a redefinition of the kilogram, probably in terms of a fixed value for the Planck constant.

  15. High mass-resolution electron-ion-ion coincidence measurements on core-excited organic molecules

    CERN Document Server

    Tokushima, T; Senba, Y; Yoshida, H; Hiraya, A

    2001-01-01

    Total electron-ion-ion coincidence measurements on core excited organic molecules have been carried out with high mass resolution by using multimode (reflectron/linear) time-of-flight mass analyzer. From the ion correlation spectra of core excited CH sub 3 OH and CD sub 3 OH, the reaction pathway to form H sub 3 sup + (D sub 3 sup +) is identified as the elimination of three H (D) atoms from the methyl group, not as the inter-group (-CH sub 3 and -OH) interactions. In a PEPIPICO spectrum of acetylacetone (CH sub 3 COCH sub 2 COCH sub 3) measured by using a reflectron TOF, correlations between ions up to mass number 70 with one-mass resolution was recorded.

  16. Urinary antihypertensive drug metabolite screening using molecular networking coupled to high-resolution mass spectrometry fragmentation

    OpenAIRE

    2016-01-01

    Introduction Mass spectrometry is the current technique of choice in studying drug metabolism. High-resolution mass spectrometry in combination with MS/MS gas-phase experiments has the potential to contribute to rapid advances in this field. However, the data emerging from such fragmentation spectral files pose challenges to downstream analysis, given their complexity and size. Objectives This study aims to detect and visualize antihypertensive drug metabolites in untargeted metabolomics expe...

  17. Gold finger formation studied by high-resolution mass spectrometry and in silico methods

    NARCIS (Netherlands)

    Laskay, Ü.A.; Garino, C.; Tsybin, Y.O.; Salassa, L.; Casini, A.

    2015-01-01

    High-resolution mass spectrometry and quantum mechanics/molecular mechanics studies were employed for characterizing the formation of two gold finger (GF) domains from the reaction of zinc fingers (ZF) with gold complexes. The influence of both the gold oxidation state and the ZF coordination sphere

  18. Gold finger formation studied by high-resolution mass spectrometry and in silico methods

    NARCIS (Netherlands)

    Laskay, Ü.A.; Garino, C.; Tsybin, Y.O.; Salassa, L.; Casini, A.

    2015-01-01

    High-resolution mass spectrometry and quantum mechanics/molecular mechanics studies were employed for characterizing the formation of two gold finger (GF) domains from the reaction of zinc fingers (ZF) with gold complexes. The influence of both the gold oxidation state and the ZF coordination sphere

  19. Automated work-flow for processing high-resolution direct infusion electrospray ionization mass spectral fingerprints

    DEFF Research Database (Denmark)

    Hansen, Michael Adsetts Edberg; Smedsgaard, Jørn

    2007-01-01

    The use of mass spectrometry (MS) is pivotal in analyses of the metabolome and presents a major challenge for subsequent data processing. While the last few years have given new high performance instruments, there has not been a comparable development in data processing. In this paper we discuss...... an automated data processing pipeline to compare large numbers of fingerprint spectra from direct infusion experiments analyzed by high resolution MS. We describe some of the intriguing problems that have to be addressed. starting with the conversion and pre-processing of the raw data to the final data...... analysis. Illustrated on the direct infusion analysis (ESI-TOF-MS) of complex mixtures the method exploits the full quality of the high-resolution present in the mass spectra. Although the method is illustrated as a new library search method for high resolution MS, we demonstrate that the output...

  20. Resolution and mass range performance in distance-of-flight mass spectrometry with a multichannel focal-plane camera detector.

    Science.gov (United States)

    Graham, Alexander W G; Ray, Steven J; Enke, Christie G; Felton, Jeremy A; Carado, Anthony J; Barinaga, Charles J; Koppenaal, David W; Hieftje, Gary M

    2011-11-15

    Distance-of-flight mass spectrometry (DOFMS) is a velocity-based mass-separation technique in which ions are separated in space along the plane of a spatially selective detector. In the present work, a solid-state charge-detection array, the focal-plane camera (FPC), was incorporated into the DOFMS platform. Use of the FPC with our DOFMS instrument resulted in improvements in analytical performance, usability, and versatility over a previous generation instrument that employed a microchannel-plate/phosphor DOF detector. Notably, FPC detection provided resolution improvements of at least a factor of 2, with typical DOF linewidths of 300 μm (R((fwhm)) = 1000). The merits of solid-state detection for DOFMS are evaluated, and methods to extend the DOFMS mass range are considered.

  1. Portable, Battery Operated Capillary Electrophoresis with Optical Isomer Resolution Integrated with Ionization Source for Mass Spectrometry

    Science.gov (United States)

    Moini, Mehdi; Rollman, Christopher M.

    2016-03-01

    We introduce a battery operated capillary electrophoresis electrospray ionization (CE/ESI) source for mass spectrometry with optical isomer separation capability. The source fits in front of low or high resolution mass spectrometers similar to a nanospray source with about the same weight and size. The source has two high voltage power supplies (±25 kV HVPS) capable of operating in forward or reverse polarity modes and powered by a 12 V rechargeable lithium ion battery with operation time of ~10 h. In ultrafast CE mode, in which short narrow capillaries (≤15 μm i.d., 15-25 cm long) and field gradients ≥1000 V/cm are used, peak widths at the base are <1 s wide. Under these conditions, the source provides high resolution separation, including optical isomer resolution in ~1 min. Using a low resolution mass spectrometer (LTQ Velos) with a scan time of 0.07 s/scan, baseline separation of amino acids and their optical isomers were achieved in ~1 min. Moreover, bovine serum albumin (BSA) was analyzed in ~1 min with 56% coverage using the data-dependent MS/MS. Using a high resolution mass spectrometer (Thermo Orbitrap Elite) with 15,000 resolution, the fastest scan time achieved was 0.15 s, which was adequate for CE-MS analysis when optical isomer separation is not required or when the optical isomers were well separated. Figures of merit including a detection limit of 2 fmol and linear dynamic range of two orders of magnitude were achieved for amino acids.

  2. A High-Resolution Time-of-Flight Mass Spectrometer for Experiments with Ultracold Gases

    CERN Document Server

    Kraft, S D; Staanum, P; Fioretti, A; Lange, J; Wester, R; Weidemüller, M; Kraft, Stephan D.; Mikosch, Jochen; Staanum, Peter; Fioretti, Andrea; Lange, Joerg; Wester, Roland; Weidemueller, Matthias

    2005-01-01

    We have realized a high-resolution time-of-flight mass spectrometer combined with a magneto-optical trap. The spectrometer enables excellent optical access to the trapped atomic cloud using properly devised acceleration and deflection electrodes. The ions are extracted along a laser axis and deflected onto an off axis detector. The setup is applied to detect atoms and molecules photoassociated from ultracold atoms. The detection is based on resonance-enhanced multi-photon ionization. The versatile setup can easily be implemented in more complex experiments with ultracold atomic and molecular gases. Mass resolution up to $m/\\Delta m_{rms} = 1000$ at the mass of $^{133}$Cs is achieved.

  3. USGS Small-scale Dataset - 100-Meter Resolution Satellite View of the Conterminous United States 201304 GeoTIFF

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — The Satellite View of the Conterminous United States map layer is a 100-meter resolution simulated natural-color image of the United States. Vegetation is generally...

  4. USGS Small-scale Dataset - 100-Meter Resolution Grayscale Shaded Relief of the Conterminous United States 201304 GeoTIFF

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — The Grayscale Shaded Relief of the Conterminous United States map layer is a 100-meter resolution grayscale shaded relief image of the United States, in an Albers...

  5. USGS Small-scale Dataset - 100-Meter Resolution Color Shaded Relief of the Conterminous United States 201304 GeoTIFF

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — The Color Shaded Relief of the Conterminous United States map layer is a 100-meter resolution color-sliced elevation image of the United States, with relief shading...

  6. USGS Small-scale Dataset - 100-Meter Resolution Color-Sliced Elevation of the Conterminous United States 201303 TIFF

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — The map layer of Color-Sliced Elevation of the Conterminous United States is a 100-meter resolution elevation image of the United States, in an Albers Equal-Area...

  7. Profiling of integral membrane proteins and their post translational modifications using high-resolution mass spectrometry

    Science.gov (United States)

    Souda, Puneet; Ryan, Christopher M.; Cramer, William A.; Whitelegge, Julian

    2011-01-01

    Integral membrane proteins pose challenges to traditional proteomics approaches due to unique physicochemical properties including hydrophobic transmembrane domains that limit solubility in aqueous solvents. A well resolved intact protein molecular mass profile defines a protein’s native covalent state including post-translational modifications, and is thus a vital measurement toward full structure determination. Both soluble loop regions and transmembrane regions potentially contain post-translational modifications that must be characterized if the covalent primary structure of a membrane protein is to be defined. This goal has been achieved using electrospray-ionization mass spectrometry (ESI-MS) with low-resolution mass analyzers for intact protein profiling, and high-resolution instruments for top-down experiments, toward complete covalent primary structure information. In top-down, the intact protein profile is supplemented by gas-phase fragmentation of the intact protein, including its transmembrane regions, using collisionally activated and/or electroncapture dissociation (CAD/ECD) to yield sequence-dependent high-resolution MS information. Dedicated liquid chromatography systems with aqueous/organic solvent mixtures were developed allowing us to demonstrate that polytopic integral membrane proteins are amenable to ESI-MS analysis, including top-down measurements. Covalent post-translational modifications are localized regardless of their position in transmembrane domains. Top-down measurements provide a more detail oriented high-resolution description of post-transcriptional and post-translational diversity for enhanced understanding beyond genomic translation. PMID:21982782

  8. Non-target screening with high-resolution mass spectrometry: critical review using a collaborative trial on water analysis.

    Science.gov (United States)

    Schymanski, Emma L; Singer, Heinz P; Slobodnik, Jaroslav; Ipolyi, Ildiko M; Oswald, Peter; Krauss, Martin; Schulze, Tobias; Haglund, Peter; Letzel, Thomas; Grosse, Sylvia; Thomaidis, Nikolaos S; Bletsou, Anna; Zwiener, Christian; Ibáñez, María; Portolés, Tania; de Boer, Ronald; Reid, Malcolm J; Onghena, Matthias; Kunkel, Uwe; Schulz, Wolfgang; Guillon, Amélie; Noyon, Naïke; Leroy, Gaëla; Bados, Philippe; Bogialli, Sara; Stipaničev, Draženka; Rostkowski, Pawel; Hollender, Juliane

    2015-08-01

    In this article, a dataset from a collaborative non-target screening trial organised by the NORMAN Association is used to review the state-of-the-art and discuss future perspectives of non-target screening using high-resolution mass spectrometry in water analysis. A total of 18 institutes from 12 European countries analysed an extract of the same water sample collected from the River Danube with either one or both of liquid and gas chromatography coupled with mass spectrometry detection. This article focuses mainly on the use of high resolution screening techniques with target, suspect, and non-target workflows to identify substances in environmental samples. Specific examples are given to emphasise major challenges including isobaric and co-eluting substances, dependence on target and suspect lists, formula assignment, the use of retention information, and the confidence of identification. Approaches and methods applicable to unit resolution data are also discussed. Although most substances were identified using high resolution data with target and suspect-screening approaches, some participants proposed tentative non-target identifications. This comprehensive dataset revealed that non-target analytical techniques are already substantially harmonised between the participants, but the data processing remains time-consuming. Although the objective of a "fully-automated identification workflow" remains elusive in the short term, important steps in this direction have been taken, exemplified by the growing popularity of suspect screening approaches. Major recommendations to improve non-target screening include better integration and connection of desired features into software packages, the exchange of target and suspect lists, and the contribution of more spectra from standard substances into (openly accessible) databases. Graphical Abstract Matrix of identification approach versus identification confidence.

  9. Energy resolution methods efficiency depending on beam source position of potassium clusters in time-of-flight mass spectrometer

    Indian Academy of Sciences (India)

    Ş Şentürk; F Demiray; O Özsoy

    2007-09-01

    Energy resolution of the time-of-flight mass spectrometer was considered. The estimations indicate that the time-lag energy focusing method provides better resolution for the parallel case while the turnaround time is more convenient for the perpendicular position. Hence the applicability of the methods used for the energy resolution depends on beam source arrangement.

  10. Analysis of kerosenes and middle distillates by medium resolution mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Castex, H.; Boulet, R.; Juguin, J.; Lepinasse, A. (Institut Francais du Petrole, Rueil-Malmaison (France))

    A mass-spectrometry analysis method derived from the ASTM D2425 standard has been developed for kerosenes and middle distillates (185-345/sup 0/C). II uses the same principle for calculating the mean carbon value to determine the approrpiate matrices. But it works with medium resolution so as to sort out the different exact masses of hydrocarbons, sulfur and oxygenated compounds, thus avoiding any prior separation by liquid chromatography (ASTM D2549). Therefore, the matrix values have been modified, and the calculation of the mean carbon value has been adapted for analyzing narrow and wide distillation cuts.

  11. New high-resolution electrostatic ion mass analyzer using time of flight

    Science.gov (United States)

    Hamilton, D. C.; Gloeckler, G.; Ipavich, F. M.; Lundgren, R. A.; Sheldon, R. B.

    1990-01-01

    The design of a high-resolution ion-mass analyzer is described, which is based on an accurate measurement of the time of flight (TOF) of ions within a region configured to produce a harmonic potential. In this device, the TOF, which is independent of ion energy, is determined from a start pulse from secondary electrons produced when the ion passes through a thin carbon foil at the entrance of the TOF region and at a stop pulse from the ion striking a microchannel plate upon exciting the region. A laboratory prototype instrument called 'VMASS' was built and was tested at the Goddard Space Flight Center electrostatic accelerator, showing a good mass resolution of the instrument. Sensors of the VMASS type will form part of the WIND Solar Wind and Suprathermal Ion experiment, the Soho mission, and the Advanced Composition Explorer.

  12. Development of high resolution simulations of the atmospheric environment using the MASS model

    Science.gov (United States)

    Kaplan, Michael L.; Zack, John W.; Karyampudi, V. Mohan

    1989-01-01

    Numerical simulations were performed with a very high resolution (7.25 km) version of the MASS model (Version 4.0) in an effort to diagnose the vertical wind shear and static stability structure during the Shuttle Challenger disaster which occurred on 28 January 1986. These meso-beta scale simulations reveal that the strongest vertical wind shears were concentrated in the 200 to 150 mb layer at 1630 GMT, i.e., at about the time of the disaster. These simulated vertical shears were the result of two primary dynamical processes. The juxtaposition of both of these processes produced a shallow (30 mb deep) region of strong vertical wind shear, and hence, low Richardson number values during the launch time period. Comparisons with the Cape Canaveral (XMR) rawinsonde indicates that the high resolution MASS 4.0 simulation more closely emulated nature than did previous simulations of the same event with the GMASS model.

  13. Early developmental stages of Ascaris lumbricoides featured by high-resolution mass spectrometry.

    Science.gov (United States)

    Melo, Carlos Fernando Odir Rodrigues; Esteves, Cibele Zanardi; de Oliveira, Rosimeire Nunes; Guerreiro, Tatiane Melina; de Oliveira, Diogo Noin; Lima, Estela de Oliveira; Miné, Júlio César; Allegretti, Silmara Marques; Catharino, Rodrigo Ramos

    2016-11-01

    Ascaris lumbricoides is responsible for a highly disseminated helminth parasitic disease, ascariosis, a relevant parasitosis that responds for great financial burden on the public health system of developing countries. In this work, metabolic fingerprinting using high-resolution mass spectrometry (HRMS) was employed to identify marker molecules from A. lumbricoides in different development stages. We have identified nine biomarkers, such as pheromones and steroidal prohormones in early stages, among other molecules in late development stages, making up four molecules for fertilized eggs, four marker molecules for first larvae (L1) and one marker molecule for third larvae (L3). Therefore, our findings indicate that this approach is suitable for biochemical characterization of A. lumbricoides development stages. Moreover, the straightforward analytical method employed, with almost no sample preparation from a complex matrix (feces) using high-resolution mass spectrometry, suggests that it is possible to seek for an easier and faster way to study animal molding processes.

  14. Fast blood flow visualization of high-resolution laser speckle imaging data using graphics processing unit.

    Science.gov (United States)

    Liu, Shusen; Li, Pengcheng; Luo, Qingming

    2008-09-15

    Laser speckle contrast analysis (LASCA) is a non-invasive, full-field optical technique that produces two-dimensional map of blood flow in biological tissue by analyzing speckle images captured by CCD camera. Due to the heavy computation required for speckle contrast analysis, video frame rate visualization of blood flow which is essentially important for medical usage is hardly achieved for the high-resolution image data by using the CPU (Central Processing Unit) of an ordinary PC (Personal Computer). In this paper, we introduced GPU (Graphics Processing Unit) into our data processing framework of laser speckle contrast imaging to achieve fast and high-resolution blood flow visualization on PCs by exploiting the high floating-point processing power of commodity graphics hardware. By using GPU, a 12-60 fold performance enhancement is obtained in comparison to the optimized CPU implementations.

  15. Introduction and Review of Hate Crime in the United States and Response of Criminal Law in China: in Addition to Resolution of Mass Incidents through Criminal Governance Concept%美国仇恨犯罪介评与我国刑法理论的应对——兼及群体性事件的刑事治理观

    Institute of Scientific and Technical Information of China (English)

    孙道萃

    2012-01-01

    美国基于偏见而产生的仇恨犯罪及立法、实施机制相当完备,但存在概念模糊、正当性不足、惩罚必要性等质疑。我国近些年群体性事件频发,但不宜引入仇恨犯罪概念。目的犯、身份犯和聚众犯罪是对美国仇恨犯罪的理论照应,因应群体性事件的根本方法是通过树立刑事治理观化解冲突。%The legislation of hate crime based on prejudice in the USA is quite complete, and it has a full-range of implementation mechanisms, while it is criticized by fuzzy concept, lack of legitimacy and justification of punishment. In recent years, mass incidents have frequently occurred in china, but the introduction of hate crime is not necessary. As a matter of fact, purpose crime, identity crime and assembled crime have already echoes to the hate crime, the substantial resolution of assembled crime is to resolve conflicts by criminal governance concept.

  16. Spatial resolution recovery utilizing multi-ray tracing and graphic processing unit in PET image reconstruction.

    Science.gov (United States)

    Liang, Yicheng; Peng, Hao

    2015-02-07

    Depth-of-interaction (DOI) poses a major challenge for a PET system to achieve uniform spatial resolution across the field-of-view, particularly for small animal and organ-dedicated PET systems. In this work, we implemented an analytical method to model system matrix for resolution recovery, which was then incorporated in PET image reconstruction on a graphical processing unit platform, due to its parallel processing capacity. The method utilizes the concepts of virtual DOI layers and multi-ray tracing to calculate the coincidence detection response function for a given line-of-response. The accuracy of the proposed method was validated for a small-bore PET insert to be used for simultaneous PET/MR breast imaging. In addition, the performance comparisons were studied among the following three cases: 1) no physical DOI and no resolution modeling; 2) two physical DOI layers and no resolution modeling; and 3) no physical DOI design but with a different number of virtual DOI layers. The image quality was quantitatively evaluated in terms of spatial resolution (full-width-half-maximum and position offset), contrast recovery coefficient and noise. The results indicate that the proposed method has the potential to be used as an alternative to other physical DOI designs and achieve comparable imaging performances, while reducing detector/system design cost and complexity.

  17. Structural characterization of suppressor lipids by high-resolution mass spectrometry

    DEFF Research Database (Denmark)

    Rovillos, Mary Joy; Pauling, Josch Konstantin; Hannibal-Bach, Hans Kristian

    2016-01-01

    RATIONALE: Suppressor lipids were originally identified in 1993 and reported to encompass six lipid classes that enable Saccharomyces cerevisiae to live without sphingolipids. Structural characterization, using non-mass spectrometric approaches, revealed that these suppressor lipids are very long...... chain fatty acid (VLCFA)-containing glycerophospholipids with polar head groups that are typically incorporated into sphingolipids. Here we report, for the first time, the structural characterization of the yeast suppressor lipids using high-resolution mass spectrometry. METHODS: Suppressor lipids were...... isolated by preparative chromatography and subjected to structural characterization using hybrid quadrupole time-of-flight and ion trap-orbitrap mass spectrometry. RESULTS: Our investigation recapitulates the overall structural features of the suppressor lipids and provides an in-depth characterization...

  18. High-mass-resolution MALDI mass spectrometry imaging of metabolites from formalin-fixed paraffin-embedded tissue.

    Science.gov (United States)

    Ly, Alice; Buck, Achim; Balluff, Benjamin; Sun, Na; Gorzolka, Karin; Feuchtinger, Annette; Janssen, Klaus-Peter; Kuppen, Peter J K; van de Velde, Cornelis J H; Weirich, Gregor; Erlmeier, Franziska; Langer, Rupert; Aubele, Michaela; Zitzelsberger, Horst; McDonnell, Liam; Aichler, Michaela; Walch, Axel

    2016-08-01

    Formalin-fixed and paraffin-embedded (FFPE) tissue specimens are the gold standard for histological examination, and they provide valuable molecular information in tissue-based research. Metabolite assessment from archived tissue samples has not been extensively conducted because of a lack of appropriate protocols and concerns about changes in metabolite content or chemical state due to tissue processing. We present a protocol for the in situ analysis of metabolite content from FFPE samples using a high-mass-resolution matrix-assisted laser desorption/ionization fourier-transform ion cyclotron resonance mass spectrometry imaging (MALDI-FT-ICR-MSI) platform. The method involves FFPE tissue sections that undergo deparaffinization and matrix coating by 9-aminoacridine before MALDI-MSI. Using this platform, we previously detected ∼1,500 m/z species in the mass range m/z 50-1,000 in FFPE samples; the overlap compared with fresh frozen samples is 72% of m/z species, indicating that metabolites are largely conserved in FFPE tissue samples. This protocol can be reproducibly performed on FFPE tissues, including small samples such as tissue microarrays and biopsies. The procedure can be completed in a day, depending on the size of the sample measured and raster size used. Advantages of this approach include easy sample handling, reproducibility, high throughput and the ability to demonstrate molecular spatial distributions in situ. The data acquired with this protocol can be used in research and clinical practice.

  19. Performance of the High Resolution, Multi-collector Helix MC Plus Noble Gas Mass Spectrometer at the Australian National University

    Science.gov (United States)

    Zhang, Xiaodong; Honda, Masahiko; Hamilton, Doug

    2016-12-01

    Performance of the Helix MC Plus noble gas mass spectrometer installed at the Australian National University (ANU) is reported. Results for sensitivity, mass discrimination and their linearity against partial pressure of noble gases, and mass resolution of the mass spectrometer are presented, and the results are compared with those of conventional noble gas mass spectrometers. The application of the five detectors on the Helix MC Plus in measuring various noble gas isotopes in multi-collector modes and the integration of the software drivers of peripheral hardware devices into the controlling program Qtegra of the mass spectrometer are discussed. High mass resolution (>1800) and mass resolving power (>8000) make this mass spectrometer unique in noble gas cosmo-geochemistry. It provides the capability to measure isobaric interference-free noble gas isotopes in multi-collector mode, significantly improves the accuracy to determine isotopic ratios, and greatly increases the efficiency of data acquisition.

  20. Performance of the High Resolution, Multi-collector Helix MC Plus Noble Gas Mass Spectrometer at the Australian National University

    Science.gov (United States)

    Zhang, Xiaodong; Honda, Masahiko; Hamilton, Doug

    2016-09-01

    Performance of the Helix MC Plus noble gas mass spectrometer installed at the Australian National University (ANU) is reported. Results for sensitivity, mass discrimination and their linearity against partial pressure of noble gases, and mass resolution of the mass spectrometer are presented, and the results are compared with those of conventional noble gas mass spectrometers. The application of the five detectors on the Helix MC Plus in measuring various noble gas isotopes in multi-collector modes and the integration of the software drivers of peripheral hardware devices into the controlling program Qtegra of the mass spectrometer are discussed. High mass resolution (>1800) and mass resolving power (>8000) make this mass spectrometer unique in noble gas cosmo-geochemistry. It provides the capability to measure isobaric interference-free noble gas isotopes in multi-collector mode, significantly improves the accuracy to determine isotopic ratios, and greatly increases the efficiency of data acquisition.

  1. 16 CFR 500.8 - Units of weight or mass and measure.

    Science.gov (United States)

    2010-01-01

    ... 16 Commercial Practices 1 2010-01-01 2010-01-01 false Units of weight or mass and measure. 500.8... SECTION 4 OF THE FAIR PACKAGING AND LABELING ACT § 500.8 Units of weight or mass and measure. (a... (15 oz)” or “Net Mass 680 g (11/2 lbs)” or “100 g e (3.5 oz).”) (b) Statements of fluid measure shall...

  2. A Simple Method for Improving the Spatial Resolution in Infrared Laser Ablation Mass Spectrometry Imaging

    Science.gov (United States)

    Hieta, Juha-Pekka; Vaikkinen, Anu; Auno, Samuli; Räikkönen, Heikki; Haapala, Markus; Scotti, Gianmario; Kopra, Jaakko; Piepponen, Petteri; Kauppila, Tiina J.

    2017-01-01

    In mass spectrometry imaging of tissues, the size of structures that can be distinguished is determined by the spatial resolution of the imaging technique. Here, the spatial resolution of IR laser ablation is markedly improved by increasing the distance between the laser and the focusing lens. As the distance between the laser and the lens is increased from 1 to 18 m, the ablation spot size decreases from 440 to 44 μm. This way, only the collimated center of the divergent laser beam is directed on the focusing lens, which results in better focusing of the beam. Part of the laser energy is lost at longer distance, but this is compensated by focusing of the radiation to a smaller area on the sample surface. The long distance can also be achieved by a set of mirrors, between which the radiation travels before it is directed to the focusing lens and the sample. This method for improving the spatial resolution can be utilized in mass spectrometry imaging of tissues by techniques that utilize IR laser ablation, such as laser ablation electrospray ionization, laser ablation atmospheric pressure photoionization, and matrix-assisted laser desorption electrospray ionization.

  3. MAINTAINING HIGH RESOLUTION MASS SPECTROMETRY CAPABILITIES FOR NATIONAL NUCLEAR SECURITY ADMINISTRATION APPLICATIONS

    Energy Technology Data Exchange (ETDEWEB)

    Wyrick, S.; Cordaro, J.; Reeves, G.; Mcintosh, J.; Mauldin, C.; Tietze, K.; Varble, D.

    2011-06-06

    The Department of Energy (DOE) National Nuclear Security Administration (NNSA) has a specialized need for analyzing low mass gas species at very high resolutions. The currently preferred analytical method is electromagnetic sector mass spectrometry. This method allows the NNSA Nuclear Security Enterprise (NSE) to resolve species of similar masses down to acceptable minimum detection limits (MDLs). Some examples of these similar masses are helium-4/deuterium and carbon monoxide/nitrogen. Through the 1980s and 1990s, there were two vendors who supplied and supported these instruments. However, with declining procurements and down turns in the economy, the supply of instruments, service and spare parts from these vendors has become less available, and in some cases, nonexistent. The largest NSE user of this capability is the Savannah River Site (SRS), located near Aiken, South Carolina. The Research and Development Engineering (R&DE) Group in the Savannah River National Laboratory (SRNL) investigated the areas of instrument support that were needed to extend the life cycle of these aging instruments. Their conclusions, as to the focus areas of electromagnetic sector mass spectrometers to address, in order of priority, were electronics, software and hardware. Over the past 3-5 years, the R&DE Group has designed state of the art electronics and software that will allow high resolution legacy mass spectrometers, critical to the NNSA mission, to be operated for the foreseeable future. The funding support for this effort has been from several sources, including the SRS Defense Programs, NNSA Readiness Campaign, Pantex Plant and Sandia National Laboratory. To date, electronics systems have been upgraded on one development system at SRNL, two production systems at Pantex and one production system at Sandia National Laboratory. An NSE working group meets periodically to review strategies going forward. The R&DE Group has also applied their work to the electronics for a

  4. Characterization of high-resolution aerosol mass spectra of primary organic aerosol emissions from Chinese cooking and biomass burning

    Directory of Open Access Journals (Sweden)

    L.-Y. He

    2010-09-01

    Full Text Available Aerosol Mass Spectrometer (AMS has proved to be a powerful tool to measure submicron particulate composition with high time resolution. Factor analysis of mass spectra (MS collected worldwide by AMS demonstrates that submicron organic aerosol (OA is usually composed of several major components, such as oxygenated (OOA, hydrocarbon-like (HOA, biomass burning (BBOA, and other primary OA. In order to help interpretation of component MS from factor analysis of ambient OA datasets, AMS measurement of different primary sources is required for comparison. Such work, however, has been very scarce in the literature, especially for high resolution MS (HR-MS measurement, which performs improved characterization by separating the ions of different elemental compositions at each m/z in comparison with unit mass resolution MS (UMR-MS measurement. In this study, primary emissions from four types of Chinese cooking (CC and six types of biomass burning (BB were simulated systemically and measured using an Aerodyne High-Resolution Time-of-Flight AMS (HR-ToF-AMS. The MS of the CC emissions show high similarity with m/z 41 and m/z 55 being the highest signals; the MS of the BB emissions also show high similarity with m/z 29 and m/z 43 being the highest signals. The MS difference between the CC and BB emissions is much bigger than that between different CC (or BB types, especially for the HR-MS. The O/C ratio of OA ranges from 0.08 to 0.13 for the CC emissions while from 0.18 to 0.26 for the BB emissions. The ions of m/z 43, m/z 44, m/z 57, and m/z 60, usually used as tracer ions in AMS measurement, were examined for their HR-MS characteristics in the CC and BB emissions. Moreover, the MS of the CC and BB emissions are also used to compare with component MS from factor analysis of ambient OA datasets observed in China, as well as with other AMS measurements of primary sources in the literature. The MS

  5. A high-resolution x-ray spectrometer for a kaon mass measurement

    Science.gov (United States)

    Phelan, Kevin; Suzuki, Ken; Zmeskal, Johann; Tortorella, Daniele; Bühler, Matthias; Hertrich, Theo

    2017-02-01

    The ASPECT consortium (Adaptable Spectrometer Enabled by Cryogenic Technology) is currently constructing a generalised cryogenic platform for cryogenic detector work which will be able to accommodate a wide range of sensors. The cryogenics system is based on a small mechanical cooler with a further adiabatic demagnetisation stage and will work with cryogenic detectors at sub-Kelvin temperatures. The commercial aim of the consortium is to produce a compact, user-friendly device with an emphasis on reliability and portability which can easily be transported for specialised on-site work, such as beam-lines or telescope facilities. The cryogenic detector platform will accommodate a specially developed cryogenic sensor, either a metallic magnetic calorimeter or a magnetic penetration-depth thermometer. The detectors will be designed to work in various temperatures regions with an emphasis on optimising the various detector resolutions for specific temperatures. One resolution target is of about 10 eV at the energies range typically created in kaonic atoms experiments (soft x-ray energies). A following step will see the introduction of continuous, high-power, sub-Kelvin cooling which will bring the cryogenic basis for a high resolution spectrometer system to the market. The scientific goal of the project will produce an experimental set-up optimised for kaon-mass measurements performing high-resolution x-ray spectroscopy on a beam-line provided foreseeably by the J-PARC (Tokai, Japan) or DAΦNE (Frascati, Italy) facilities.

  6. High-resolution mass-selective UV spectroscopy of pseudoephedrine: evidence for conformer-specific fragmentation.

    Science.gov (United States)

    Karaminkov, R; Chervenkov, S; Delchev, V; Neusser, H J

    2011-09-01

    Using resonance-enhanced two-photon ionization spectroscopy with mass resolution of jet-cooled molecules, a low-resolution S(1) ← S(0) vibronic spectrum of pseudoephedrine was recorded at the mass channels of three distinct fragments with m/z = 58, 71, and 85. Two of the fragments, with m/z = 71 and 85, are observed for the first time for this molecule. The vibronic spectra recorded at different mass channels feature different patterns, implying that they originate from different conformers in the cold molecular beam, following conformer-specific fragmentation pathways. Highly resolved spectra of all prominent vibronic features were measured, and from their analysis based on genetic algorithms, the molecular parameters of the conformers giving rise to the respective bands have been determined. Comparing the experimental results with those obtained from high-level ab initio quantum chemistry calculations, the observed prominent vibronic bands have been assigned to originate from four distinct conformers. The conformers are separated into two groups that have different fragmentation pathways determined by the different intramolecular interactions.

  7. Determination of Trace Elements in High Purity Gold by High Resolution Inductively Coupled Plasma Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    XIE Hualin; HUANG Kelong; NIE Xidu; FU Liang

    2009-01-01

    Trace elements were determined in high purity gold by high resolution inductively coupled plasma mass spectrometry(HR-ICP-MS).Sample were decomposed by aqua regia.To overcome some potentially problematic spectral interference,measurements were acquired in both medium and high resolution modes.The matrix effects due to the presence of excessive HCl and Au were evaluated.The optimum conditions for the determination was tested and discussed.The standard addition method was employed for quantitative analysis.The detection limits range from 0.01 μg/g to 0.28 μg/g depending on the elements.The method is accurate,quick and convenient.It has been applied to the determination of trace elements in high purity gold with satisfactory results.

  8. 13C labeling analysis of sugars by high resolution-mass spectrometry for metabolic flux analysis.

    Science.gov (United States)

    Acket, Sébastien; Degournay, Anthony; Merlier, Franck; Thomasset, Brigitte

    2017-02-14

    Metabolic flux analysis is particularly complex in plant cells because of highly compartmented metabolism. Analysis of free sugars is interesting because it provides data to define fluxes around hexose, pentose, and triose phosphate pools in different compartment. In this work, we present a method to analyze the isotopomer distribution of free sugars labeled with carbon 13 using a liquid chromatography-high resolution mass spectrometry, without derivatized procedure, adapted for Metabolic flux analysis. Our results showed a good sensitivity, reproducibility and better accuracy to determine isotopic enrichments of free sugars compared to our previous methods [5, 6].

  9. Seed oil polyphenols: rapid and sensitive extraction method and high resolution-mass spectrometry identification.

    Science.gov (United States)

    Koubaa, Mohamed; Mhemdi, Houcine; Vorobiev, Eugène

    2015-05-01

    Phenolic content is a primary parameter for vegetables oil quality evaluation, and directly involved in the prevention of oxidation and oil preservation. Several methods have been reported in the literature for polyphenols extraction from seed oil but the approaches commonly used remain manually handled. In this work, we propose a rapid and sensitive method for seed oil polyphenols extraction and identification. For this purpose, polyphenols were extracted from Opuntia stricta Haw seed oil, using high frequency agitation, separated, and then identified using a liquid chromatography-high resolution mass spectrometry method. Our results showed good sensitivity and reproducibility of the developed methods.

  10. Mass Hierarchy Resolution in Reactor Anti-neutrino Experiments: Parameter Degeneracies and Detector Energy Response

    Energy Technology Data Exchange (ETDEWEB)

    X. Qian, D. A. Dwyer, R. D. McKeown, P. Vogel, W. Wang, C. Zhang`

    2013-02-01

    Determination of the neutrino mass hierarchy using a reactor neutrino experiment at ∼60  km is analyzed. Such a measurement is challenging due to the finite detector resolution, the absolute energy scale calibration, and the degeneracies caused by current experimental uncertainty of |Δm{sub 32}{sup 2}|. The standard {chi}{sup 2} method is compared with a proposed Fourier transformation method. In addition, we show that for such a measurement to succeed, one must understand the nonlinearity of the detector energy scale at the level of a few tenths of percent.

  11. Glycation promoted by dynamic high pressure microfluidisation pretreatment revealed by high resolution mass spectrometry.

    Science.gov (United States)

    Huang, Xiaoqin; Tu, Zongcai; Wang, Hui; Zhang, Qiuting; Hu, Yueming; Zhang, Lan; Niu, Peipei; Shi, Yan; Xiao, Hui

    2013-12-01

    The effect of dynamic high pressure microfluidisation (DHPM) pretreatment on the glycation of bovine serum albumin (BSA) was investigated. A detailed glycation map was obtained from high resolution mass spectrometry. Without DHPM pretreatment, only 7 glycation sites were identified, whereas the numbers were increased to 10, 11 and 11 when BSA-glucose was pretreated with DHPM at 50, 100 and 200 MPa, respectively, suggesting that DHPM pretreatment can significantly promote the Maillard reaction. Average degree of substitution per peptide molecule BSA (DSP) was used to further evaluate the glycation level under various DHPM conditions. All the DHPM pretreated samples exhibited elevated glycation level compared to the un-pretreated sample. With 100 MPa DHPM pretreatment, the protein showed the most significantly enhanced glycation extent. In addition, our results suggest that Maillard-type glycation followed by mass spectrometry analysis can be used to study the conformational changes when proteins are disturbed by external forces.

  12. High Resolution Weak Lensing Mass-Mapping Combining Shear and Flexion

    CERN Document Server

    Lanusse, Francois; Leonard, Adrienne; Pires, Sandrine

    2016-01-01

    We propose a new mass-mapping algorithm, specifically designed to recover small-scale information from a combination of gravitational shear and flexion. Including flexion allows us to supplement the shear on small scales in order to increase the sensitivity to substructures and the overall resolution of the convergence map without relying on strong lensing constraints. In order to preserve all available small scale information, we avoid any binning of the irregularly sampled input shear and flexion fields and treat the mass-mapping problem as a general ill-posed inverse problem, regularised using a robust multi-scale wavelet sparsity prior. The resulting algorithm incorporates redshift, reduced shear, and reduced flexion measurements for individual galaxies and is made highly efficient by the use of fast Fourier estimators. We test our reconstruction method on a set of realistic weak lensing simulations corresponding to typical HST/ACS cluster observations and demonstrate our ability to recover substructures ...

  13. Protein hydrogen exchange measured at single-residue resolution by electron transfer dissociation mass spectrometry

    DEFF Research Database (Denmark)

    Rand, Kasper D; Zehl, Martin; Jensen, Ole Nørregaard

    2009-01-01

    Because of unparalleled sensitivity and tolerance to protein size, mass spectrometry (MS) has become a popular method for measuring the solution hydrogen (1H/2H) exchange (HX) of biologically relevant protein states. While incorporated deuterium can be localized to different regions by pepsin...... the HX of individual amide linkages in the amyloidogenic protein beta2-microglobulin. A comparison of the deuterium levels of 60 individual backbone amides of beta2-microglobulin measured by HX-ETD-MS analysis to the corresponding values measured by NMR spectroscopy shows an excellent correlation......-phase hydrogen (1H/2H) migration (i.e., hydrogen scrambling). This article demonstrates that ETD can be implemented in a mass spectrometric method to monitor the conformational dynamics of proteins in solution at single-residue resolution....

  14. Mass spectrometry of pertrimethylsilyl oligosaccharides containing fructose units

    NARCIS (Netherlands)

    Vliegenthart, J.F.G.; Kamerling, J.P.; Vink, Jan; Ridder, J.J. de

    1972-01-01

    Mass spectra of 6 TMS-disaccharides of type aldohexosyl-(1-> x)-fructose, in which x varies from 1 to 6, were compared and could be divided into two main groups i.e. (1 ar 1), (1 ar 2) disaccharides and (1 ar 3), (1 ar 4), (1 ar 5), (1 ar 6) disaccharides. Within both groups a further differentiatio

  15. Atmospheric-Pressure Chemical Ionization Tandem Mass Spectrometry (APGC/MS/MS) an Alternative to High-Resolution Mass Spectrometry (HRGC/HRMS) for the Determination of Dioxins

    NARCIS (Netherlands)

    Bavel, Van Bert; Geng, Dawei; Cherta, Laura; Nácher-Mestre, Jaime; Portolés, Tania; Ábalos, Manuela; Sauló, Jordi; Abad, Esteban; Dunstan, Jody; Jones, Rhys; Kotz, Alexander; Winterhalter, Helmut; Malisch, Rainer; Traag, Wim; Hagberg, Jessika; Ericson Jogsten, Ingrid; Beltran, Joaquim; Hernández, Félix

    2015-01-01

    The use of a new atmospheric-pressure chemical ionization source for gas chromatography (APGC) coupled with a tandem quadrupole mass spectrometry (MS/MS) system, as an alternative to high-resolution mass spectrometry (HRMS), for the determination of PCDDs/PCDFs is described. The potential of usin

  16. Division of high resolution sequence stratigraphy units with wavelet transform of logs in Dagang Oilfield

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Division of high resolution sequence stratigraphy units based on wavelet transform of logging data is found to be good at identifying subtle cycles of geological process in Kongnan area of Dagang Oilfield. The analysis of multi-scales gyre of formation with 1-D continuous Dmey wavelet transform of log curve (GR) and 1-D discrete Daubechies wavelet transform of log curve (Rt) all make the division of sequence interfaces more objective and precise, which avoids the artificial influence with core analysis and the uncertainty with seismic data and core analysis.

  17. Detection and quantification of proteins in clinical samples using high resolution mass spectrometry.

    Science.gov (United States)

    Gallien, Sebastien; Domon, Bruno

    2015-06-15

    Quantitative proteomics has benefited from the recent development of mass spectrometers capable of high-resolution and accurate-mass (HR/AM) measurements. While targeted experiments are routinely performed on triple quadrupole instruments in selected reaction monitoring (SRM; often referred as multiple reaction monitoring, MRM) mode, the quadrupole-orbitrap mass spectrometers allow quantification in MS/MS mode, also known as parallel reaction monitoring (PRM). This technique is characterized by higher selectivity and better confidence in the assignment of the precursor and fragment ions, and thus translates into an improved analytical performance. More fundamentally, PRM introduces a change of the overall paradigm of targeted experiments, by the decoupling of the acquisition and data processing. They rely on two distinct steps, with a simplified acquisition method in conjunction with a flexible, iterative, post-acquisition data processing. This account describes in detail the different steps of a PRM experiment, which include the design of the acquisition method, the confirmation of the identity of the analytes founded upon a full MS/MS fragmentation pattern, and the quantification based on the extraction of specific fragment ions (selected post-acquisition) using tight mass tolerance. The different types of PRM experiments, defined as large-scale screening or precise targeted quantification using calibrated internal standards, together with the considerations on the selection of experimental parameters are discussed.

  18. USGS Small-scale Dataset - 100-Meter Resolution Tree Canopy of the Conterminous United States 201301 GeoTIFF

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — This map layer contains tree canopy data for the conterminous United States, in an Albers Equal-Area Conic projection and at a resolution of 100 meters. The tree...

  19. USGS Small-scale Dataset - 100-Meter Resolution Impervious Surface of the Conterminous United States 201301 TIFF

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — This map layer contains impervious surface data for the conterminous United States, in an Albers Equal-Area Conic projection and at a resolution of 100 meters. The...

  20. United States Air Force Role in Mass Atrocity Response Operations

    Science.gov (United States)

    2012-05-17

    through the lens of their own perspective. They cannot view the world objectively because of their own preconceptions : history, prejudices, ideology...initial stages of the genocide. Similarly, the RC-135’s ability to detect and locate those stations would provide the perfect target for strikes having...all levels. Air Force unit exercises would integrate air power, focusing on those specific tasks required in a MARO. These training exercises , in

  1. Ion Mobility Spectrometry - High Resolution LTQ-Orbitrap Mass Spectrometry for Analysis of Homemade Explosives

    Science.gov (United States)

    Hagan, Nathan; Goldberg, Ilana; Graichen, Adam; St. Jean, Amanda; Wu, Ching; Lawrence, David; Demirev, Plamen

    2017-08-01

    The detailed chemical characterization of homemade explosives (HMEs) and other chemicals that can mimic or mask the presence of explosives is important for understanding and improving the performance of commercial instrumentation used for explosive detection. To that end, an atmospheric-pressure drift tube ion mobility spectrometry (IMS) instrument has been successfully coupled to a commercial tandem mass spectrometry (MS) system. The tandem MS system is comprised of a linear ion trap and a high resolution Orbitrap analyzer. This IMS-MS combination allows extensive characterization of threat chemical compounds, including HMEs, and complex real-world background chemicals that can interfere with detection. Here, the composition of ion species originating from a specific HME, erythritol tetranitrate, has been elucidated using accurate mass measurements, isotopic ratios, and tandem MS. Gated IMS-MS and high-resolution MS have been used to identify minor impurities that can be indicative of the HME source and/or synthesis route. Comparison between data obtained on the IMS/MS system and on commercial stand-alone IMS instruments used as explosive trace detectors (ETDs) has also been performed. Such analysis allows better signature assignments of threat compounds, modified detection algorithms, and improved overall ETD performance.

  2. An Automated Platform for High-Resolution Tissue Imaging Using Nanospray Desorption Electrospray Ionization Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Lanekoff, Ingela T.; Heath, Brandi S.; Liyu, Andrey V.; Thomas, Mathew; Carson, James P.; Laskin, Julia

    2012-10-02

    An automated platform has been developed for acquisition and visualization of mass spectrometry imaging (MSI) data using nanospray desorption electrospray ionization (nano-DESI). The new system enables robust operation of the nano-DESI imaging source over many hours. This is achieved by controlling the distance between the sample and the probe by mounting the sample holder onto an automated XYZ stage and defining the tilt of the sample plane. This approach is useful for imaging of relatively flat samples such as thin tissue sections. Custom software called MSI QuickView was developed for visualization of large data sets generated in imaging experiments. MSI QuickView enables fast visualization of the imaging data during data acquisition and detailed processing after the entire image is acquired. The performance of the system is demonstrated by imaging rat brain tissue sections. High resolution mass analysis combined with MS/MS experiments enabled identification of lipids and metabolites in the tissue section. In addition, high dynamic range and sensitivity of the technique allowed us to generate ion images of low-abundance isobaric lipids. High-spatial resolution image acquired over a small region of the tissue section revealed the spatial distribution of an abundant brain metabolite, creatine, in the white and gray matter that is consistent with the literature data obtained using magnetic resonance spectroscopy.

  3. High-resolution mass models of dwarf galaxies from LITTLE THINGS

    CERN Document Server

    Oh, Se-Heon; Brinks, Elias; Elmegreen, Bruce G; Schruba, Andreas; Walter, Fabian; Rupen, Michael P; Young, Lisa M; Simpson, Caroline E; Johnson, Megan; Herrmann, Kimberly A; Ficut-Vicas, Dana; Cigan, Phil; Heesen, Volker; Ashley, Trisha; Zhang, Hong-Xin

    2015-01-01

    We present high-resolution rotation curves and mass models of 26 dwarf galaxies from LITTLE THINGS. LITTLE THINGS is a high-resolution Very Large Array HI survey for nearby dwarf galaxies in the local volume within 11 Mpc. The rotation curves of the sample galaxies derived in a homogeneous and consistent manner are combined with Spitzer archival 3.6 micron and ancillary optical U, B, and V images to construct mass models of the galaxies. We decompose the rotation curves in terms of the dynamical contributions by baryons and dark matter halos, and compare the latter with those of dwarf galaxies from THINGS as well as Lambda CDM SPH simulations in which the effect of baryonic feedback processes is included. Being generally consistent with THINGS and simulated dwarf galaxies, most of the LITTLE THINGS sample galaxies show a linear increase of the rotation curve in their inner regions, which gives shallower logarithmic inner slopes alpha of their dark matter density profiles. The mean value of the slopes of the 2...

  4. Advances in liquid chromatography-high-resolution mass spectrometry for quantitative and qualitative environmental analysis.

    Science.gov (United States)

    Aceña, Jaume; Stampachiacchiere, Serena; Pérez, Sandra; Barceló, Damià

    2015-08-01

    This review summarizes the advances in environmental analysis by liquid chromatography-high-resolution mass spectrometry (LC-HRMS) during the last decade and discusses different aspects of their application. LC-HRMS has become a powerful tool for simultaneous quantitative and qualitative analysis of organic pollutants, enabling their quantitation and the search for metabolites and transformation products or the detection of unknown compounds. LC-HRMS provides more information than low-resolution (LR) MS for each sample because it can accurately determine the mass of the molecular ion and its fragment ions if it can be used for MS-MS. Another advantage is that the data can be processed using either target analysis, suspect screening, retrospective analysis, or non-target screening. With the growing popularity and acceptance of HRMS analysis, current guidelines for compound confirmation need to be revised for quantitative and qualitative purposes. Furthermore, new commercial software and user-built libraries are required to mine data in an efficient and comprehensive way. The scope of this critical review is not to provide a comprehensive overview of the many studies performed with LC-HRMS in the field of environmental analysis, but to reveal its advantages and limitations using different workflows.

  5. High Resolution Studies of the Origins of Polyatomic Ions in Inductively Coupled Plasma-Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Ferguson, Jill Wisnewski [Iowa State Univ., Ames, IA (United States)

    2006-01-01

    The inductively coupled plasma (ICP) is an atmospheric pressure ionization source. Traditionally, the plasma is sampled via a sampler cone. A supersonic jet develops behind the sampler, and this region is pumped down to a pressure of approximately one Torr. A skimmer cone is located inside this zone of silence to transmit ions into the mass spectrometer. The position of the sampler and skimmer cones relative to the initial radiation and normal analytical zones of the plasma is key to optimizing the useful analytical signal [1]. The ICP both atomizes and ionizes the sample. Polyatomic ions form through ion-molecule interactions either in the ICP or during ion extraction [l]. Common polyatomic ions that inhibit analysis include metal oxides (MO+), adducts with argon, the gas most commonly used to make up the plasma, and hydride species. While high resolution devices can separate many analytes from common interferences, this is done at great cost in ion transmission efficiency--a loss of 99% when using high versus low resolution on the same instrument [2]. Simple quadrupole devices, which make up the bulk of ICP-MS instruments in existence, do not present this option. Therefore, if the source of polyatomic interferences can be determined and then manipulated, this could potentially improve the figures of merit on all ICP-MS devices, not just the high resolution devices often utilized to study polyatomic interferences.

  6. Assessment of meat authenticity using bioinformatics, targeted peptide biomarkers and high-resolution mass spectrometry.

    Science.gov (United States)

    Ruiz Orduna, Alberto; Husby, Erik; Yang, Charles T; Ghosh, Dipankar; Beaudry, Francis

    2015-01-01

    In recent years a significant increase of food fraud has been observed, ranging from false label claims to the use of additives and fillers to increase profitability. Recently in 2013 horse and pig DNAs were detected in beef products sold from several retailers. Mass spectrometry (MS) has become the workhorse in protein research, and the detection of marker proteins could serve for both animal species and tissue authentication. Meat species authenticity is performed in this paper using a well-defined proteogenomic annotation, carefully chosen surrogate tryptic peptides and analysis using a hybrid quadrupole-Orbitrap MS. Selected mammalian meat samples were homogenised and proteins were extracted and digested with trypsin. The samples were analysed using a high-resolution MS. Chromatography was achieved using a 30-min linear gradient along with a BioBasic C8 100 × 1 mm column at a flow rate of 75 µl min(-1). The MS was operated in full-scan high resolution and accurate mass. MS/MS spectra were collected for selected proteotypic peptides. Muscular proteins were methodically analysed in silico in order to generate tryptic peptide mass lists and theoretical MS/MS spectra. Following a comprehensive bottom-up proteomic analysis, we detected and identified a proteotypic myoglobin tryptic peptide (120-134) for each species with observed m/z below 1.3 ppm compared with theoretical values. Moreover, proteotypic peptides from myosin-1, myosin-2 and β-haemoglobin were also identified. This targeted method allowed comprehensive meat speciation down to 1% (w/w) of undesired product.

  7. High-resolution Orbitrap™-based mass spectrometry for rapid detection of peanuts in nuts.

    Science.gov (United States)

    Monaci, Linda; De Angelis, Elisabetta; Bavaro, Simona L; Pilolli, Rosa

    2015-01-01

    Peanut represents one of the most harmful allergenic foods capable of triggering severe and sometimes lethal reactions in allergic consumers upon ingestion of even small amounts. Several proteins capable of inducing allergic reactions that have been recognised by patients' IgE antibodies have been identified from this nut source. Methods mainly based on ELISA assays have been developed in order to detect peanuts in several food commodities. In addition LC-MS/MS methods based on different mass analysers have also been devised for tracing peanut contamination in different foods achieving low limits of detection. The applicability of a benchtop high-resolution Exactive™ mass spectrometer has never been investigated for the rapid screening of peanut contamination in complex food matrices like mixtures of nuts. We report in this paper the design of suitable peanut markers and the development of an high-resolution Orbitrap™ mass spectrometer-based method for peanut detection in a mixture of nuts species. With this aim, different types of samples were prepared: (1) nuts-based powder made up of a mixture of hazelnuts, pistachios, almonds and walnuts; and (2) nuts powder fortified with peanuts. Different levels of fortifications were produced and the applicability of the method was tested. Finally, a subset of six peptides fulfilling specific analytical requirements was chosen to check the suitability of the method tailored to the detection of peanuts in nuts-based products, and two of them, peptides VYD and WLG, were selected as quantitative markers. The method proved to be a suitable screening tool to assess the presence of traces of peanuts in other tree nuts with a limit of detection as low as 4 µg of peanuts proteins or 26 µg of peanuts in 1 g of matrix.

  8. Direct Analysis in Real Time (DART) of an Organothiophosphate at Ultrahigh Resolution by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry and Tandem Mass Spectrometry.

    Science.gov (United States)

    Prokai, Laszlo; Stevens, Stanley M

    2016-01-16

    Direct analysis in real time (DART) is a recently developed ambient ionization technique for mass spectrometry to enable rapid and sensitive analyses with little or no sample preparation. After swab-based field sampling, the organothiophosphate malathion was analyzed using DART-Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry (MS) and tandem mass spectrometry (MS/MS). Mass resolution was documented to be over 800,000 in full-scan MS mode and over 1,000,000 for an MS/MS product ion produced by collision-induced dissociation of the protonated analyte. Mass measurement accuracy below 1 ppm was obtained for all DART-generated ions that belonged to the test compound in the mass spectra acquired using only external mass calibration. This high mass measurement accuracy, achievable at present only through FTMS, was required for unequivocal identification of the corresponding molecular formulae.

  9. Analysis of high mass resolution PTR-TOF mass spectra from 1,3,5-trimethylbenzene (TMB environmental chamber experiments

    Directory of Open Access Journals (Sweden)

    M. Müller

    2011-09-01

    Full Text Available A series of 1,3,5-trimethylbenzene (TMB photo-oxidation experiments was performed in the 27-m3 Paul Scherrer Institute environmental chamber under various NOx conditions. A University of Innsbruck prototype high resolution Proton Transfer Reaction Time-of-Flight Mass Spectrometer (PTR-TOF was used for measurements of gas and particulate phase organics. The gas phase mass spectrum displayed ~200 ion signals during the TMB photo-oxidation experiments. Molecular formulas CNmHnNoOp were determined and ion signals were separated and grouped according to their C, O and N numbers. This allowed to determine the time evolution of the O:C ratio and of the average carbon oxidation state OSC of the reaction mixture. Both quantities were compared with master chemical mechanism (MCMv3.1 simulations. The O:C ratio in the particle phase was about twice the O:C ratio in the gas phase. Average carbon oxidation states of secondary organic aerosol (SOA samples OSCSOA were in the range of −0.34 to −0.31, in agreement with expected average carbon oxidation states of fresh SOA (OSC = −0.5 − 0.

  10. A high-resolution mass spectrometer to measure atmospheric ion composition

    Directory of Open Access Journals (Sweden)

    H. Junninen

    2010-02-01

    Full Text Available In this paper we present recent achievements on developing and testing a tool to detect the composition of ambient ions in the mass/charge range up to 2000 Th. The instrument is an Atmospheric Pressure Interface Time-of-Flight Mass Spectrometer (APi-TOF, Tofwerk AG. Its mass accuracy is better than 0.002%, and the mass resolving power is 3000 Th/Th. In the data analysis, a new efficient Matlab based set of programs (tofTools were developed, tested and used. The APi-TOF was tested both in laboratory conditions and applied to outdoor air sampling in Helsinki at the SMEAR III station. Transmission efficiency calibrations showed a throughput of 0.1–0.5% in the range 100–1300 Th for positive ions, and linearity over 3 orders of magnitude in concentration was determined. In the laboratory tests the APi-TOF detected sulphuric acid-ammonia clusters in high concentration from a nebulised sample illustrating the potential of the instrument in revealing the role of sulphuric acid clusters in atmospheric new particle formation. The APi-TOF features a high enough accuracy, resolution and sensitivity for the determination of the composition of atmospheric small ions although the total concentration of those ions is typically only 400–2000 cm-3. The atmospheric ions were identified based on their exact masses, utilizing Kendrick analysis and correlograms as well as narrowing down the potential candidates based on their proton affinities as well isotopic patterns. In Helsinki during day-time the main negative ambient small ions were inorganic acids and their clusters. The positive ions were more complex, the main compounds were (polyalkyl pyridines and – amines. The APi-TOF provides a near universal interface for atmospheric pressure sampling, and this key feature will be utilized in future laboratory and field studies.

  11. Molecular composition of organic aerosols in central Amazonia: an ultra-high-resolution mass spectrometry study

    Science.gov (United States)

    Kourtchev, Ivan; Godoi, Ricardo H. M.; Connors, Sarah; Levine, James G.; Archibald, Alex T.; Godoi, Ana F. L.; Paralovo, Sarah L.; Barbosa, Cybelli G. G.; Souza, Rodrigo A. F.; Manzi, Antonio O.; Seco, Roger; Sjostedt, Steve; Park, Jeong-Hoo; Guenther, Alex; Kim, Saewung; Smith, James; Martin, Scot T.; Kalberer, Markus

    2016-09-01

    The Amazon Basin plays key role in atmospheric chemistry, biodiversity and climate change. In this study we applied nanoelectrospray (nanoESI) ultra-high-resolution mass spectrometry (UHRMS) for the analysis of the organic fraction of PM2.5 aerosol samples collected during dry and wet seasons at a site in central Amazonia receiving background air masses, biomass burning and urban pollution. Comprehensive mass spectral data evaluation methods (e.g. Kendrick mass defect, Van Krevelen diagrams, carbon oxidation state and aromaticity equivalent) were used to identify compound classes and mass distributions of the detected species. Nitrogen- and/or sulfur-containing organic species contributed up to 60 % of the total identified number of formulae. A large number of molecular formulae in organic aerosol (OA) were attributed to later-generation nitrogen- and sulfur-containing oxidation products, suggesting that OA composition is affected by biomass burning and other, potentially anthropogenic, sources. Isoprene-derived organosulfate (IEPOX-OS) was found to be the most dominant ion in most of the analysed samples and strongly followed the concentration trends of the gas-phase anthropogenic tracers confirming its mixed anthropogenic-biogenic origin. The presence of oxidised aromatic and nitro-aromatic compounds in the samples suggested a strong influence from biomass burning especially during the dry period. Aerosol samples from the dry period and under enhanced biomass burning conditions contained a large number of molecules with high carbon oxidation state and an increased number of aromatic compounds compared to that from the wet period. The results of this work demonstrate that the studied site is influenced not only by biogenic emissions from the forest but also by biomass burning and potentially other anthropogenic emissions from the neighbouring urban environments.

  12. Evaluation of gas chromatography – electron ionization – full scan high resolution Orbitrap mass spectrometry for pesticide residue analysis

    NARCIS (Netherlands)

    Mol, Hans G.J.; Tienstra, Marc; Zomer, Paul

    2016-01-01

    Gas chromatography with electron ionization and full scan high resolution mass spectrometry with an Orbitrap mass analyzer (GC-EI-full scan Orbitrap HRMS) was evaluated for residue analysis. Pesticides in fruit and vegetables were taken as an example application. The relevant aspects for GC-MS

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

    Directory of Open Access Journals (Sweden)

    Park Kwon

    2006-10-01

    Full Text Available Abstract 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.

  14. Development and Evaluation of High-Resolution Climate Simulations Over the Mountainous Northeastern United States

    Science.gov (United States)

    Winter, Jonathan M.; Beckage, Brian; Bucini, Gabriela; Horton, Radley M.; Clemins, Patrick J.

    2016-01-01

    The mountain regions of the northeastern United States are a critical socioeconomic resource for Vermont, New York State, New Hampshire, Maine, and southern Quebec. While global climate models (GCMs) are important tools for climate change risk assessment at regional scales, even the increased spatial resolution of statistically downscaled GCMs (commonly approximately 1/ 8 deg) is not sufficient for hydrologic, ecologic, and land-use modeling of small watersheds within the mountainous Northeast. To address this limitation, an ensemble of topographically downscaled, high-resolution (30"), daily 2-m maximum air temperature; 2-m minimum air temperature; and precipitation simulations are developed for the mountainous Northeast by applying an additional level of downscaling to intermediately downscaled (1/ 8 deg) data using high-resolution topography and station observations. First, observed relationships between 2-m air temperature and elevation and between precipitation and elevation are derived. Then, these relationships are combined with spatial interpolation to enhance the resolution of intermediately downscaled GCM simulations. The resulting topographically downscaled dataset is analyzed for its ability to reproduce station observations. Topographic downscaling adds value to intermediately downscaled maximum and minimum 2-m air temperature at high-elevation stations, as well as moderately improves domain-averaged maximum and minimum 2-m air temperature. Topographic downscaling also improves mean precipitation but not daily probability distributions of precipitation. Overall, the utility of topographic downscaling is dependent on the initial bias of the intermediately downscaled product and the magnitude of the elevation adjustment. As the initial bias or elevation adjustment increases, more value is added to the topographically downscaled product.

  15. Rock Mass Characterization by High-Resolution Sonic and GSI Borehole Logging

    Science.gov (United States)

    Agliardi, F.; Sapigni, M.; Crosta, G. B.

    2016-11-01

    We investigate the relationships between the in situ P-wave velocity (Vp) of rock masses, measured by borehole acoustic logging, and their Geological Strength Index (GSI), to support a reliable assessment of equivalent continuum rock mass properties at depth. We quantified both Vp and GSI in three deep boreholes drilled in a crystalline core complex of the central Italian Alps. The boreholes were driven up to 400 m in depth and provided high-quality drill cores in gneiss, schist and metasedimentary rocks with variable lithology. Geological and geomechanical logging was carried out for over 800 m of cores, and acoustic logging was performed for more than 600 m of borehole length. High-resolution core logging in terms of GSI was obtained using an original quantitative approach. Candidate empirical correlation functions linking Vp and GSI were tested by a two-step statistical analysis of the experimental dataset, including outlier removal and nonlinear regression analysis. We propose a sigmoid Vp-GSI equation valid over a depth range between 100 and 400 m. This accounts for extremely variable lithological, weathering and rock mass damage conditions, complementing existing shallow-depth approaches and showing potential for practical applications in different engineering settings.

  16. Ultrahigh resolution mass spectrometric characterization of organic aerosol from European and Chinese cities

    Science.gov (United States)

    Wang, Kai; Huang, Ru-Jin; Hoffmann, Thorsten

    2016-04-01

    Organic aerosol constitutes a substantial fraction (20-90%) of submicrometer aerosol mass, playing an important role in air quality and human health. Over the past few years, ultra-high resolution mass spectrometry (UHRMS) has been applied to elucidate the chemical composition of ambient aerosols. However, most of the UHRMS studies used direct infusion without prior separation by liquid chromatography, which may cause the loss of individual compound information and interference problems. In the present study, urban ambient aerosol with particle diameter Beijing, China, respectively. Two pretreatment procedures were applied to extract the organic compounds from the filter samples: One method uses a mixture of acetonitrile and water, the other uses pure water and prepared for the extraction of humic-like substances. The extracts were analyzed by ultra-high-performance liquid chromatography coupled with an Orbitrap mass spectrometer in both negative and the positive modes. The effects of pretreatment procedures on the characterization of organic aerosol and the city-wise difference in chemical composition of organic aerosol will be discussed in detail.

  17. Elemental analysis of aerosol organic nitrates with electron ionization high-resolution mass spectrometry

    Directory of Open Access Journals (Sweden)

    A. W. Rollins

    2009-10-01

    Full Text Available Four hydroxynitrates (R(OHR'ONO2 representative of atmospheric volatile organic compound (VOC oxidation products were synthesized, nebulized and sampled into an Aerodyne High Resolution Time of Flight Aerosol Mass Spectrometer (HR-ToF-AMS. The resulting mass spectrum was used to evaluate calibration factors for elemental analysis of organic nitrates by AMS, and to determine the distribution of nitrogen in the detected fragments in a search for an AMS signature of organic nitrates. We find that 30% of the detected nitrogen mass is in the NO+ and NO2+ fragments, 12% at NHx+ fragments, 5% at CxHyOzN+ fragments, and 53% at various CxHyN+ fragments. Elemental analysis indicated that nitrogen was detected with higher efficiency than carbon and hydrogen, but oxygen was detected with reduced efficiency compared to previously reported results for a suite of organics which did not include organic nitrates. The results are used to suggest the maximum corrections to ambient O:C and N:C ratios based on AMS measurements.

  18. Chemical Diversity and Complexity of Scotch Whisky as Revealed by High-Resolution Mass Spectrometry

    Science.gov (United States)

    Kew, Will; Goodall, Ian; Clarke, David; Uhrín, Dušan

    2017-01-01

    Scotch Whisky is an important product, both culturally and economically. Chemically, Scotch Whisky is a complex mixture, which comprises thousands of compounds, the nature of which are largely unknown. Here, we present a thorough overview of the chemistry of Scotch Whisky as observed by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Eighty-five whiskies, representing the majority of Scotch Whisky produced and sold, were analyzed by untargeted high-resolution mass spectrometry. Thousands of chemical formulae were assigned for each sample based on parts-per-billion mass accuracy of FT-ICR MS spectra. For the first time, isotopic fine structure analysis was used to confirm the assignment of high molecular weight CHOS species in Scotch Whisky. The assigned spectra were compared using a number of visualization techniques, including van Krevelen diagrams, double bond equivalence (DBE) plots, as well as heteroatomic compound class distributions. Additionally, multivariate analysis, including PCA and OPLS-DA, was used to interpret the data, with key compounds identified for discriminating between types of whisky (blend or malt) or maturation wood type. FT-ICR MS analysis of Scotch Whisky was shown to be of significant potential in further understanding of the complexity of mature spirit drinks and as a tool for investigating the chemistry of the maturation processes.

  19. Advances in high-resolution mass spectrometry based on metabolomics studies for food--a review.

    Science.gov (United States)

    Rubert, Josep; Zachariasova, Milena; Hajslova, Jana

    2015-01-01

    Food authenticity becomes a necessity for global food policies, since food placed in the market without fail has to be authentic. It has always been a challenge, since in the past minor components, called also markers, have been mainly monitored by chromatographic methods in order to authenticate the food. Nevertheless, nowadays, advanced analytical methods have allowed food fingerprints to be achieved. At the same time they have been also combined with chemometrics, which uses statistical methods in order to verify food and to provide maximum information by analysing chemical data. These sophisticated methods based on different separation techniques or stand alone have been recently coupled to high-resolution mass spectrometry (HRMS) in order to verify the authenticity of food. The new generation of HRMS detectors have experienced significant advances in resolving power, sensitivity, robustness, extended dynamic range, easier mass calibration and tandem mass capabilities, making HRMS more attractive and useful to the food metabolomics community, therefore becoming a reliable tool for food authenticity. The purpose of this review is to summarise and describe the most recent metabolomics approaches in the area of food metabolomics, and to discuss the strengths and drawbacks of the HRMS analytical platforms combined with chemometrics.

  20. Molecular Chemistry of Organic Aerosols Through the Application of High Resolution Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Nizkorodov, Serguei; Laskin, Julia; Laskin, Alexander

    2011-01-05

    Understanding of molecular composition and fundamental chemical transformations of organic aerosols (OA) during their formation and aging is both a major challenge and the area of greatest uncertainty in atmospheric research. Particularly little is known about fundamental relationship between the chemical composition and physicochemical properties of OA, their atmospheric history, evolution, and impact on the environment. Ambient soft-ionization methods combined with high-resolution mass spectrometry (HR-MS) analysis provide detailed information on the molecular content of OA that is pivotal for improved understanding of their complex composition, multi-phase aging chemistry, direct (light absorption and scattering) and indirect (aerosol-cloud interactions) effects on atmospheric radiation and climate, and health effects. The HR-MS methods can detect thousands of individual OA constituents at once, provide their elemental formulae from accurate mass measurements, and provide structural information based on tandem mass spectrometry. Integration with additional analytical tools, such as chromatography and UV/Vis absorption spectroscopy, makes it possible to further separate OA compounds by their polarity and ability to absorb solar radiation. The goal of this perspective is to describe modern HR-MS methods, review recent applications to field and laboratory studies of OA, and explain how the information obtained from HR-MS methods can be translated into improved understanding of OA chemistry.

  1. Enhancing non-refractory aerosol apportionment from an urban industrial site through receptor modelling of complete high time-resolution aerosol mass spectra

    Directory of Open Access Journals (Sweden)

    M. L. McGuire

    2014-02-01

    Full Text Available Receptor modelling was performed on quadrupole unit mass resolution aerosol mass spectrometer (Q-AMS sub-micron particulate matter (PM chemical speciation measurements from Windsor, Ontario, an industrial city situated across the Detroit River from Detroit, Michigan. Aerosol and trace gas measurements were collected on board Environment Canada's CRUISER mobile laboratory. Positive matrix factorization (PMF was performed on the AMS full particle-phase mass spectrum (PMFFull MS encompassing both organic and inorganic components. This approach was compared to the more common method of analysing only the organic mass spectra (PMFOrg MS. PMF of the full mass spectrum revealed that variability in the non-refractory sub-micron aerosol concentration and composition was best explained by six factors: an amine-containing factor (Amine; an ammonium sulphate and oxygenated organic aerosol containing factor (Sulphate-OA; an ammonium nitrate and oxygenated organic aerosol containing factor (Nitrate-OA; an ammonium chloride containing factor (Chloride; a hydrocarbon-like organic aerosol (HOA factor; and a moderately oxygenated organic aerosol factor (OOA. PMF of the organic mass spectrum revealed three factors of similar composition to some of those revealed through PMFFull MS: Amine, HOA and OOA. Including both the inorganic and organic mass proved to be a beneficial approach to analysing the unit mass resolution AMS data for several reasons. First, it provided a method for potentially calculating more accurate sub-micron PM mass concentrations, particularly when unusual factors are present, in this case, an Amine factor. As this method does not rely on a priori knowledge of chemical species, it circumvents the need for any adjustments to the traditional AMS species fragmentation patterns to account for atypical species, and can thus lead to more complete factor profiles. It is expected that this method would be even more useful for HR-ToF-AMS data, due to

  2. Factor analysis of combined organic and inorganic aerosol mass spectra from high resolution aerosol mass spectrometer measurements

    Directory of Open Access Journals (Sweden)

    Y. L. Sun

    2012-05-01

    Full Text Available The high resolution mass spectra of organic and inorganic aerosols from aerosol mass spectrometer (AMS measurements were first combined into positive matrix factorization (PMF analysis to investigate the sources and evolution processes of atmospheric aerosols. The new approach is able to study the mixing of organic aerosols (OA and inorganic species, the acidity of OA factors, and the fragment ion patterns related to photochemical processing. In this study, PMF analysis of the unified AMS spectral matrices resolved 8 factors for the submicron aerosols measured at Queens College in New York City in summer 2009. The hydrocarbon-like OA (HOA and cooking OA (COA contain very minor inorganic species, indicating the different sources and mixing characteristics between primary OA and secondary species. The two factors that are primarily ammonium sulfate (SO4-OA and ammonium nitrate (NO3-OA, respectively, are overall neutralized, of which the OA in SO4-OA shows the highest oxidation state (O/C = 0.69 among OA factors. The semi-volatile oxygenated OA comprises two components, i.e., a less oxidized (LO-OOA and a more oxidized (MO-OOA. The MO-OOA represents a local photochemical product with the diurnal profile exhibiting a pronounced noon peak, consistent with those of formaldehyde (HCHO and Ox (= O3+NO2. The much higher NO+/NO2+ fragment ion ratio in MO-OOA than that from ammonium nitrate alone provides evidence for the formation of organic nitrates. The amine-related nitrogen-enriched OA (NOA contains ~25% of acidic inorganic salts, elucidating the formation of secondary OA from amines in acidic environments. The size distributions derived from 3-dimensional size-resolved mass spectra show distinct diurnal evolving behaviors for different OA factors, but overall a progressing evolution from smaller to larger particle mode as a function of oxidation states

  3. High-angular resolution observations towards OMC-2 FIR 4: Dissecting an intermediate-mass protocluster

    Science.gov (United States)

    López-Sepulcre, A.; Taquet, V.; Sánchez-Monge, Á.; Ceccarelli, C.; Dominik, C.; Kama, M.; Caux, E.; Fontani, F.; Fuente, A.; Ho, P. T. P.; Neri, R.; Shimajiri, Y.

    2013-08-01

    Context. Intermediate-mass stars are an important ingredient of our Galaxy and a key to understanding how high- and low-mass stars form in clusters. One of the closest known young intermediate-mass protoclusters is OMC-2 FIR 4, which is located at a distance of 420 pc in Orion. This region is one of the few where the complete 500-2000 GHz spectrum has been observed with the heterodyne spectrometer HIFI on board the Herschel satellite, and unbiased spectral surveys at 0.8, 1, 2, and 3 mm have been obtained with the JCMT and IRAM 30-m telescopes. Aims: We aim to disentangle the core multiplicity, to investigate the morphology of this region in order to study the formation of a low- and intermediate-mass protostar cluster, and to aid in interpretation of the single-dish line profiles already in our hands. Methods: We used the IRAM Plateau de Bure Interferometer to image OMC-2 FIR 4 in the 2-mm continuum emission, as well as in DCO+(2-1), DCN(2-1), C34S(3-2), and several CH3OH lines. In addition, we analysed observations of the NH3(1, 1) and (2, 2) inversion transitions that used the Very Large Array of the NRAO. The resulting maps have an angular resolution that allows us to resolve structures of 5″, which is equivalent to ~2000 AU. Results: Our observations reveal three spatially resolved sources within OMC-2 FIR 4, of one or several solar masses each, with hints of further unresolved substructure within them. Two of these sources have elongated shapes and are associated with dust continuum emission peaks, thus likely containing at least one molecular core each. One of them also displays radio continuum emission, which may be attributed to a young B3-B4 star that dominates the overall luminosity output of the region. The third identified source displays a DCO+(2-1) emission peak and weak dust continuum emission. Its higher abundance of DCO+ relative to the other two regions suggests a lower temperature, hence its possible association with either a younger low-mass

  4. Current use of high-resolution mass spectrometry in the environmental sciences

    Energy Technology Data Exchange (ETDEWEB)

    Hernandez, F.; Sancho, J.V.; Ibanez, M.; Portoles, T. [University Jaume I, Research Institute for Pesticides and Water, Castellon (Spain); Abad, E.; Mattioli, L. [IDAEA-CSIC, Laboratory of Dioxins, Department of Environmental Chemistry, Barcelona (Spain)

    2012-05-15

    During the last two decades, mass spectrometry (MS) has been increasingly used in the environmental sciences with the objective of investigating the presence of organic pollutants. MS has been widely coupled with chromatographic techniques, both gas chromatography (GC) and liquid chromatography (LC), because of their complementary nature when facing a broad range of organic pollutants of different polarity and volatility. A clear trend has been observed, from the very popular GC-MS with a single quadrupole mass analyser, to tandem mass spectrometry (MS-MS) and, more recently, high-resolution mass spectrometry (HRMS). For years GC has been coupled to HR magnetic sector instruments, mostly for dioxin analysis, although in the last ten years there has been growing interest in HRMS with time-of-flight (TOF) and Orbitrap mass analyzers, especially in LC-MS analysis. The increasing interest in the use of HRMS in the environmental sciences is because of its suitability for both targeted and untargeted analysis, owing to its sensitivity in full-scan acquisition mode and high mass accuracy. With the same instrument one can perform a variety of tasks: pre- and post-target analysis, retrospective analysis, discovery of metabolite and transformation products, and non-target analysis. All these functions are relevant to the environmental sciences, in which the analyst encounters thousands of different organic contaminants. Thus, wide-scope screening of environmental samples is one of the main applications of HRMS. This paper is a critical review of current use of HRMS in the environmental sciences. Needless to say, it is not the intention of the authors to summarise all contributions of HRMS in this field, as in classic descriptive reviews, but to give an overview of the main characteristics of HRMS, its strong potential in environmental mass spectrometry and the trends observed over the last few years. Most of the literature has been acquired since 2005, coinciding with the

  5. In-depth glycoproteomic characterization of γ-conglutin by high-resolution accurate mass spectrometry.

    Directory of Open Access Journals (Sweden)

    Silvia Schiarea

    Full Text Available The molecular characterization of bioactive food components is necessary for understanding the mechanisms of their beneficial or detrimental effects on human health. This study focused on γ-conglutin, a well-known lupin seed N-glycoprotein with health-promoting properties and controversial allergenic potential. Given the importance of N-glycosylation for the functional and structural characteristics of proteins, we studied the purified protein by a mass spectrometry-based glycoproteomic approach able to identify the structure, micro-heterogeneity and attachment site of the bound N-glycan(s, and to provide extensive coverage of the protein sequence. The peptide/N-glycopeptide mixtures generated by enzymatic digestion (with or without N-deglycosylation were analyzed by high-resolution accurate mass liquid chromatography-multi-stage mass spectrometry. The four main micro-heterogeneous variants of the single N-glycan bound to γ-conglutin were identified as Man2(Xyl (Fuc GlcNAc2, Man3(Xyl (Fuc GlcNAc2, GlcNAcMan3(Xyl (Fuc GlcNAc2 and GlcNAc 2Man3(Xyl (Fuc GlcNAc2. These carry both core β1,2-xylose and core α1-3-fucose (well known Cross-Reactive Carbohydrate Determinants, but corresponding fucose-free variants were also identified as minor components. The N-glycan was proven to reside on Asn131, one of the two potential N-glycosylation sites. The extensive coverage of the γ-conglutin amino acid sequence suggested three alternative N-termini of the small subunit, that were later confirmed by direct-infusion Orbitrap mass spectrometry analysis of the intact subunit.

  6. Atmospheric Oxidation of Squalene: Molecular Study Using COBRA Modeling and High-Resolution Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Fooshee, David R.; Aiona, Paige K.; Laskin, Alexander; Laskin, Julia; Nizkorodov, Sergey; Baldi, Pierre

    2015-10-22

    Squalene is a major component of skin and plant surface lipids, and is known to be present at high concentrations in indoor dust. Its high reactivity toward ozone makes it an important ozone sink and a natural protectant against atmospheric oxidizing agents. While the volatile products of squalene ozonolysis are known, the condensed-phase products have not been characterized. We present an analysis of condensed-phase products resulting from an extensive oxidation of squalene by ozone probed by electrospray ionization (ESI) high-resolution mass spectrometry (HR-MS). A complex distribution of nearly 1,300 peaks assignable to molecular formulas is observed in direct infusion positive ion mode ESI mass spectra. The distribution of peaks in the mass spectra suggests that there are extensive cross-coupling reactions between hydroxy-carbonyl products of squalene ozonolysis. To get additional insights into the mechanism, we apply a Computational Brewing Application (COBRA) to simulate the oxidation of squalene in the presence of ozone, and compare predicted results with those observed by the HR-MS experiments. The system predicts over one billion molecular structures between 0-1450 Da, which correspond to about 27,000 distinct elemental formulas. Over 83% of the squalene oxidation products inferred from the mass spectrometry data are matched by the simulation. Simulation indicates a prevalence of peroxy groups, with hydroxyl and ether groups being the second-most important O-containing functional groups formed during squalene oxidation. These highly oxidized products of squalene ozonolysis may accumulate on indoor dust and surfaces, and contribute to their redox capacity.

  7. In-Depth Glycoproteomic Characterization of γ-Conglutin by High-Resolution Accurate Mass Spectrometry

    Science.gov (United States)

    Schiarea, Silvia; Arnoldi, Lolita; Fanelli, Roberto; De Combarieu, Eric; Chiabrando, Chiara

    2013-01-01

    The molecular characterization of bioactive food components is necessary for understanding the mechanisms of their beneficial or detrimental effects on human health. This study focused on γ-conglutin, a well-known lupin seed N-glycoprotein with health-promoting properties and controversial allergenic potential. Given the importance of N-glycosylation for the functional and structural characteristics of proteins, we studied the purified protein by a mass spectrometry-based glycoproteomic approach able to identify the structure, micro-heterogeneity and attachment site of the bound N-glycan(s), and to provide extensive coverage of the protein sequence. The peptide/N-glycopeptide mixtures generated by enzymatic digestion (with or without N-deglycosylation) were analyzed by high-resolution accurate mass liquid chromatography–multi-stage mass spectrometry. The four main micro-heterogeneous variants of the single N-glycan bound to γ-conglutin were identified as Man2(Xyl) (Fuc) GlcNAc2, Man3(Xyl) (Fuc) GlcNAc2, GlcNAcMan3(Xyl) (Fuc) GlcNAc2 and GlcNAc 2Man3(Xyl) (Fuc) GlcNAc2. These carry both core β1,2-xylose and core α1-3-fucose (well known Cross-Reactive Carbohydrate Determinants), but corresponding fucose-free variants were also identified as minor components. The N-glycan was proven to reside on Asn131, one of the two potential N-glycosylation sites. The extensive coverage of the γ-conglutin amino acid sequence suggested three alternative N-termini of the small subunit, that were later confirmed by direct-infusion Orbitrap mass spectrometry analysis of the intact subunit. PMID:24069245

  8. Amino acid analysis in micrograms of meteorite sample by nanoliquid chromatography-high-resolution mass spectrometry.

    Science.gov (United States)

    Callahan, Michael P; Martin, Mildred G; Burton, Aaron S; Glavin, Daniel P; Dworkin, Jason P

    2014-03-07

    Amino acids and their enantiomers in a 360 microgram sample of Murchison meteorite were unambiguously identified and quantified using chemical derivatization and nanoliquid chromatography coupled to nanoelectrospray ionization high resolution orbitrap mass spectrometry techniques. The distribution and abundance of amino acids were similar to past studies of Murchison meteorite but the samples used here were three orders of magnitude lower. The analytical method was also highly sensitive, and some amino acid reference standards were successfully detected at a level of ∼200 attomoles (on column). These results may open up the possibility for investigating other less studied, sample-limited extraterrestrial samples (e.g., micrometeorites, interplanetary dust particles, and cometary particles) for biologically-relevant organic molecules.

  9. High Angular Resolution Observations of Four Candidate BLAST High-Mass Starless Cores

    CERN Document Server

    Olmi, Luca; Chapin, Edward L; Gibb, Andrew; Hofner, Peter; Martin, Peter G; Poventud, Carlos M

    2010-01-01

    We discuss high-angular resolution observations of ammonia toward four candidate high-mass starless cores (HMSCs). The cores were identified by the Balloon-borne Large Aperture Submillimeter Telescope (BLAST) during its 2005 survey of the Vulpecula region where 60 compact sources were detected simultaneously at 250, 350, and 500 micron. Four of these cores, with no IRAS-PSC or MSX counterparts, were observed with the NRAO Very Large Array (VLA) in the NH3(1,1) and (2,2) spectral lines. Our observations indicate that the four cores are cold (Tk <~ 14K) and show a filamentary and/or clumpy structure. They also show a significant velocity substructure within ~1km/s. The four BLAST cores appear to be colder and more quiescent than other previously observed HMSC candidates, suggesting an earlier stage of evolution.

  10. Saffron authentication based on liquid chromatography high resolution tandem mass spectrometry and multivariate data analysis.

    Science.gov (United States)

    Rubert, Josep; Lacina, Ondrej; Zachariasova, Milena; Hajslova, Jana

    2016-08-01

    Saffron is one of the oldest and most expensive spices, which is often target of fraudulent activities. In this research, a new strategy of saffron authentication based on metabolic fingerprinting was developed. In the first phase, a solid liquid extraction procedure was optimized, the main aim was to isolate as maximal representation of small molecules contained in saffron as possible. In the second step, a detection method based on liquid chromatography coupled with high-resolution mass spectrometry was developed. Initially, principal component analysis (PCA) revealed clear differences between saffron cultivated and packaged in Spain, protected designation of origin (PDO), and saffron packaged in Spain of unknown origin, labeled Spanish saffron. Afterwards, orthogonal partial least square discriminant analysis (OPLS-DA) was favorably used to discriminate between Spanish saffron. The tentative identification of markers showed glycerophospholipids and their oxidized lipids were significant markers according to their origin.

  11. Resolution of isomeric multi-ruthenated porphyrins by travelling wave ion mobility mass spectrometry.

    Science.gov (United States)

    Lalli, Priscila M; Iglesias, Bernardo A; Deda, Daiana K; Toma, Henrique E; de Sa, Gilberto F; Daroda, Romeu J; Araki, Koiti; Eberlin, Marcos N

    2012-02-15

    The ability of travelling wave ion mobility mass spectrometry (TWIM-MS) to resolve cationic meta/para and cis/trans isomers of mono-, di-, tri- and tetra-ruthenated supramolecular porphyrins was investigated. All meta isomers were found to be more compact than the para isomers and therefore mixtures of all isomeric pairs could be properly resolved with baseline or close to baseline peak-to-peak resolution (R(p-p)). Di-substituted cis/trans isomers were found, however, to present very similar drift times and could not be resolved. N(2) and CO(2) were tested as the drift gas, and similar α but considerably better values of R(p) and R(p-p) were always observed for CO(2).

  12. Confirmatory analysis of firocoxib in bovine milk by rapid resolution liquid chromatography tandem mass spectrometry.

    Science.gov (United States)

    Dowling, Geraldine; Gallo, Pasquale; Regan, Liam

    2009-02-15

    A rapid method has been developed to analyse for firocoxib (FIRO) residue in bovine milk. Milk samples were extracted with acetonitrile and sample extracts were purified on Evolute ABN solid phase extraction cartridges. Aliquots were analysed by rapid resolution liquid chromatography tandem mass spectrometry (RRLC-MS/MS). The method was validated in bovine milk, according to the criteria defined in Commission Decision 2002/657/EC. The decision limit (CCalpha) was 1.18ng/mL and for the detection capability a (CCbeta) value of 2.02ng/mL was obtained. The measurement uncertainty of the method was 27%. Fortifying bovine milk samples (n=18) in three separate assays, show the accuracy of the method to be between 96 and 105%. The precision of the method, expressed as RSD values for the within-lab reproducibility at the three levels of fortification (5, 7.5 and 10ng/mL) was less than 11% respectively.

  13. Reference Standardization for Mass Spectrometry and High-resolution Metabolomics Applications to Exposome Research.

    Science.gov (United States)

    Go, Young-Mi; Walker, Douglas I; Liang, Yongliang; Uppal, Karan; Soltow, Quinlyn A; Tran, ViLinh; Strobel, Frederick; Quyyumi, Arshed A; Ziegler, Thomas R; Pennell, Kurt D; Miller, Gary W; Jones, Dean P

    2015-12-01

    The exposome is the cumulative measure of environmental influences and associated biological responses throughout the lifespan, including exposures from the environment, diet, behavior, and endogenous processes. A major challenge for exposome research lies in the development of robust and affordable analytic procedures to measure the broad range of exposures and associated biologic impacts occurring over a lifetime. Biomonitoring is an established approach to evaluate internal body burden of environmental exposures, but use of biomonitoring for exposome research is often limited by the high costs associated with quantification of individual chemicals. High-resolution metabolomics (HRM) uses ultra-high resolution mass spectrometry with minimal sample preparation to support high-throughput relative quantification of thousands of environmental, dietary, and microbial chemicals. HRM also measures metabolites in most endogenous metabolic pathways, thereby providing simultaneous measurement of biologic responses to environmental exposures. The present research examined quantification strategies to enhance the usefulness of HRM data for cumulative exposome research. The results provide a simple reference standardization protocol in which individual chemical concentrations in unknown samples are estimated by comparison to a concurrently analyzed, pooled reference sample with known chemical concentrations. The approach was tested using blinded analyses of amino acids in human samples and was found to be comparable to independent laboratory results based on surrogate standardization or internal standardization. Quantification was reproducible over a 13-month period and extrapolated to thousands of chemicals. The results show that reference standardization protocol provides an effective strategy that will enhance data collection for cumulative exposome research. In principle, the approach can be extended to other types of mass spectrometry and other analytical methods.

  14. A brief history of the unit of mass: continuity of successive definitions of the kilogram

    Science.gov (United States)

    Davis, Richard S.; Barat, Pauline; Stock, Michael

    2016-10-01

    The very first definition of the kilogram was in terms of a constant of nature, although this idea could not be fully realized at the end of the 18th century. Instead the kilogram was defined by an artefact whose mass was made to approximate as closely as possible a physical constant with unit kg m-3—the maximum density of distilled water at atmospheric pressure. For the next two centuries, mass comparators improved greatly as did the materials from which artefacts could be constructed. These improvements put tighter constraints on the realization of a non-artefact definition of the kilogram. However, it is now expected that the goal of redefining the kilogram in terms of fundamental constants will be achieved in 2018. We present a history of the kilogram with emphasis on continuity of this unit of mass each time it has been redefined and the stability of a unit defined by the mass of an artefact.

  15. Indexing Permafrost Soil Organic Matter Degradation Using High-Resolution Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Mann, Benjamin F.; Chen, Hong-Mei; Herndon, Elizabeth M.; Chu, Rosalie K.; Tolic, Nikola; Portier, Evan; Chowdhury, Taniya R.; Robinson, Errol W.; Callister, Stephen J.; Wullschleger, Stan D.; Graham, David E.; Liang, Liyuan; Gu, Baohua

    2015-06-12

    Microbial degradation of soil organic matter (SOM) is a key process for terrestrial carbon cycling, although the molecular details of these transformations remain unclear. This study reports the application of ultrahigh resolution mass spectrometry to profile the molecular composition of SOM and its degradation during a simulated warming experiment. A soil sample, collected near Barrow, Alaska, USA, was subjected to a 40-day incubation under anoxic conditions and analyzed before and after the incubation to determine changes of SOM composition. A CHO index based on molecular C, H, and O data was utilized to codify SOM components according to their observed degradation potentials. Compounds with a CHO index score between –1 and 0 in a water-soluble fraction (WSF) demonstrated high degradation potential, with a highest shift of CHO index occurred in the N-containing group of compounds, while similar stoichiometries in a base-soluble fraction (BSF) did not. Additionally, compared with the classical H:C vs O:C van Krevelen diagram, CHO index allowed for direct visualization of the distribution of heteroatoms such as N in the identified SOM compounds. We demonstrate that CHO index is useful not only in characterizing arctic SOM at the molecular level but also enabling quantitative description of SOM degradation, thereby facilitating incorporation of the high resolution MS datasets to future mechanistic models of SOM degradation and prediction of greenhouse gas emissions.

  16. Indexing Permafrost Soil Organic Matter Degradation Using High-Resolution Mass Spectrometry.

    Directory of Open Access Journals (Sweden)

    Benjamin F Mann

    Full Text Available Microbial degradation of soil organic matter (SOM is a key process for terrestrial carbon cycling, although the molecular details of these transformations remain unclear. This study reports the application of ultrahigh resolution mass spectrometry to profile the molecular composition of SOM and its degradation during a simulated warming experiment. A soil sample, collected near Barrow, Alaska, USA, was subjected to a 40-day incubation under anoxic conditions and analyzed before and after the incubation to determine changes of SOM composition. A CHO index based on molecular C, H, and O data was utilized to codify SOM components according to their observed degradation potentials. Compounds with a CHO index score between -1 and 0 in a water-soluble fraction (WSF demonstrated high degradation potential, with a highest shift of CHO index occurred in the N-containing group of compounds, while similar stoichiometries in a base-soluble fraction (BSF did not. Additionally, compared with the classical H:C vs O:C van Krevelen diagram, CHO index allowed for direct visualization of the distribution of heteroatoms such as N in the identified SOM compounds. We demonstrate that CHO index is useful not only in characterizing arctic SOM at the molecular level but also enabling quantitative description of SOM degradation, thereby facilitating incorporation of the high resolution MS datasets to future mechanistic models of SOM degradation and prediction of greenhouse gas emissions.

  17. Indexing Permafrost Soil Organic Matter Degradation Using High-Resolution Mass Spectrometry

    Science.gov (United States)

    Herndon, Elizabeth M.; Chu, Rosalie K.; Tolic, Nikola; Portier, Evan F.; Roy Chowdhury, Taniya; Robinson, Errol W.; Callister, Stephen J.; Wullschleger, Stan D.; Graham, David E.; Liang, Liyuan; Gu, Baohua

    2015-01-01

    Microbial degradation of soil organic matter (SOM) is a key process for terrestrial carbon cycling, although the molecular details of these transformations remain unclear. This study reports the application of ultrahigh resolution mass spectrometry to profile the molecular composition of SOM and its degradation during a simulated warming experiment. A soil sample, collected near Barrow, Alaska, USA, was subjected to a 40-day incubation under anoxic conditions and analyzed before and after the incubation to determine changes of SOM composition. A CHO index based on molecular C, H, and O data was utilized to codify SOM components according to their observed degradation potentials. Compounds with a CHO index score between –1 and 0 in a water-soluble fraction (WSF) demonstrated high degradation potential, with a highest shift of CHO index occurred in the N-containing group of compounds, while similar stoichiometries in a base-soluble fraction (BSF) did not. Additionally, compared with the classical H:C vs O:C van Krevelen diagram, CHO index allowed for direct visualization of the distribution of heteroatoms such as N in the identified SOM compounds. We demonstrate that CHO index is useful not only in characterizing arctic SOM at the molecular level but also enabling quantitative description of SOM degradation, thereby facilitating incorporation of the high resolution MS datasets to future mechanistic models of SOM degradation and prediction of greenhouse gas emissions. PMID:26068586

  18. Imaging ion and molecular transport at subcellular resolution by secondary ion mass spectrometry

    Science.gov (United States)

    Chandra, Subhash; Morrison, George H.

    1995-05-01

    The transport of K+, Na+, and Ca2+ were imaged in individual cells with a Cameca IMS-3f ion microscope. Strict cryogenic frozen freeze-dry sample preparations were employed. Ion redistribution artifacts in conventional chemical preparations are discussed. Cryogenically prepared freeze-fractured freeze-dried cultured cells allowed the three-dimensional ion microscopic imaging of elements. As smaller structures in calcium images can be resolved with the 0.5 [mu]m spatial resolution, correlative techniques are needed to confirm their identity. The potentials of reflected light microscopy, scanning electron microscopy and laser scanning confocal microscopy are discussed for microfeature recognition in freeze-fractured freeze-dried cells. The feasibility of using frozen freeze-dried cells for imaging molecular transport at subcellular resolution was tested. Ion microscopy successfully imaged the transport of the isotopically tagged (13C, 15N) amino acid, -arginine. The labeled amino acid was imaged at mass 28 with a Cs+ primary ion beam as the 28(13C15N)- species. After a 4 h exposure of LLC-PK1 kidney cells to 4 mM labeled arginine, the amino acid was localized throughout the cell with a preferential incorporation into the nucleus and nucleolus. An example is also shown of the ion microscopic imaging of sodium borocaptate, an experimental therapeutic drug for brain tumors, in cryogenically prepared frozen freeze-dried Swiss 3T3 cells.

  19. Indexing Permafrost Soil Organic Matter Degradation Using High-Resolution Mass Spectrometry.

    Science.gov (United States)

    Mann, Benjamin F; Chen, Hongmei; Herndon, Elizabeth M; Chu, Rosalie K; Tolic, Nikola; Portier, Evan F; Roy Chowdhury, Taniya; Robinson, Errol W; Callister, Stephen J; Wullschleger, Stan D; Graham, David E; Liang, Liyuan; Gu, Baohua

    2015-01-01

    Microbial degradation of soil organic matter (SOM) is a key process for terrestrial carbon cycling, although the molecular details of these transformations remain unclear. This study reports the application of ultrahigh resolution mass spectrometry to profile the molecular composition of SOM and its degradation during a simulated warming experiment. A soil sample, collected near Barrow, Alaska, USA, was subjected to a 40-day incubation under anoxic conditions and analyzed before and after the incubation to determine changes of SOM composition. A CHO index based on molecular C, H, and O data was utilized to codify SOM components according to their observed degradation potentials. Compounds with a CHO index score between -1 and 0 in a water-soluble fraction (WSF) demonstrated high degradation potential, with a highest shift of CHO index occurred in the N-containing group of compounds, while similar stoichiometries in a base-soluble fraction (BSF) did not. Additionally, compared with the classical H:C vs O:C van Krevelen diagram, CHO index allowed for direct visualization of the distribution of heteroatoms such as N in the identified SOM compounds. We demonstrate that CHO index is useful not only in characterizing arctic SOM at the molecular level but also enabling quantitative description of SOM degradation, thereby facilitating incorporation of the high resolution MS datasets to future mechanistic models of SOM degradation and prediction of greenhouse gas emissions.

  20. Forty Years of the United Nations General Assembly Resolution 3379 (XXX on Zionism and Racism: the Brazilian Vote as an instance of United States - Brazil Relations

    Directory of Open Access Journals (Sweden)

    NORMA BREDA DOS SANTOS

    2015-12-01

    Full Text Available Abstract In 1975, Brazil voted in favor of the United Nations General Assembly resolution 3379 (XXX, equating Zionism with a form of racism. Focusing on the decision-making process of president Ernesto Geisel's (1974-1979 foreign policy, "responsible pragmatism", this article discusses how the ultimate decision to vote in favor of resolution was taken taking into account mainly US-Brazil relationship.

  1. Developing a multiscale, multi-resolution agent-based brain tumor model by graphics processing units

    Directory of Open Access Journals (Sweden)

    Zhang Le

    2011-12-01

    Full Text Available Abstract Multiscale agent-based modeling (MABM has been widely used to simulate Glioblastoma Multiforme (GBM and its progression. At the intracellular level, the MABM approach employs a system of ordinary differential equations to describe quantitatively specific intracellular molecular pathways that determine phenotypic switches among cells (e.g. from migration to proliferation and vice versa. At the intercellular level, MABM describes cell-cell interactions by a discrete module. At the tissue level, partial differential equations are employed to model the diffusion of chemoattractants, which are the input factors of the intracellular molecular pathway. Moreover, multiscale analysis makes it possible to explore the molecules that play important roles in determining the cellular phenotypic switches that in turn drive the whole GBM expansion. However, owing to limited computational resources, MABM is currently a theoretical biological model that uses relatively coarse grids to simulate a few cancer cells in a small slice of brain cancer tissue. In order to improve this theoretical model to simulate and predict actual GBM cancer progression in real time, a graphics processing unit (GPU-based parallel computing algorithm was developed and combined with the multi-resolution design to speed up the MABM. The simulated results demonstrated that the GPU-based, multi-resolution and multiscale approach can accelerate the previous MABM around 30-fold with relatively fine grids in a large extracellular matrix. Therefore, the new model has great potential for simulating and predicting real-time GBM progression, if real experimental data are incorporated.

  2. High-resolution infrared detector and its electronic unit for space application

    Science.gov (United States)

    Meftah, M.; Montmessin, F.; Korablev, O.; Trokhimovsky, A.; Poiet, G.; Bel, J.-B.

    2015-05-01

    High-resolution infrared detector is used extensively for military and civilian purposes. Military applications include target acquisition, surveillance, night vision, and tracking. Civilian applications include, among others, scientific observations. For our space systems, we want to use the products developed by SOFRADIR Company. Thus, we have developed a space electronic unit that is used to control the high-resolution SCORPIO-MW infrared detector, which has a format of 640×512 pixels with 15μm×15μm pixel pitch. The detector within microelectronics based on infrared mid-wave (MW) complementary metal oxide semiconductors (CMOS) uses a micro-cooler in order to keep its temperature around 100 K. The standard wavelength range (3 to 5μm) is adapted to the 2.2 to 4.3μm wavelength range thanks to adaptation of the optical interface of the detector and with an antireflection coating. With our electronic system, we can acquire 3 images per second. To increase the signal to noise ratio, we have the opportunity to make a summation of 15 frames per image. Through this article, we will describe the space electronic system that we have developed in order to achieve space observations (e.g. Atmospheric Chemistry Suite package for ExoMars Trace Gas Orbiter).

  3. High-Resolution Mass Spectroscopic Analysis of Secondary Organic Aerosol Generated by Ozonolysis of Isoprene

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen, Tran B; Bateman, Adam P; Bones, David L; Nizkorodov, Serguei; Laskin, Julia; Laskin, Alexander

    2010-02-01

    The chemical composition of secondary organic aerosol (SOA) generated from the ozonolysis of isoprene (C5H8) in the presence of an OH scavenger was examined using high-resolution electrospray ionization mass spectrometry (ESI-MS). The chemical composition of SOA is complex, with more than 1000 assigned peaks observed in the positive and negative ion mode spectra. Only a small fraction of peaks corresponds to known products of isoprene oxidation, such as pyruvic acid, glycolic acid, methylglyoxal, etc. The absolute majority of the detected peaks correspond to highly oxidized oligomeric constituents of SOA, with an average O:C molar ratio of ~0.6. The corresponding organic mass (OM) to organic oxygen (OO) ratio is OM/OO ~2.4. Approximately 8% of oxygen atoms in SOA are in the form of peroxides as quantified with an iodide test. Double bond equivalency (DBE) factors, representing the sum of all double bonds and rings, increase by 1 for every 2-3 additional carbon atoms in the molecule. The prevalent oligomer building blocks are therefore carbonyls or carboxylic acids with a C2-C3 skeleton. Kendrick analysis suggests that simple aldehydes, specifically formaldehyde, acetaldehyde, and methylglyoxal can serve as monomeric building blocks in the observed oligomers. The large number of reactive functional groups, especially organic peroxides and carbonyls, suggests that isoprene/O3 SOA should be prone to chemical and photochemical aging.

  4. High angular resolution observations towards OMC-2 FIR 4: Dissecting an intermediate-mass protocluster

    CERN Document Server

    López-Sepulcre, A; Sánchez-Monge, Á; Ceccarelli, C; Dominik, C; Kama, M; Caux, E; Fontani, F; Fuente, A; Ho, P T P; Neri, R; Shimajiri, Y

    2013-01-01

    OMC-2 FIR 4 is one of the closest known young intermediate-mass protoclusters, located at a distance of 420 pc in Orion. This region is one of the few where the complete 500-2000 GHz spectrum has been observed with the heterodyne spectrometer HIFI on board the Herschel satellite, and unbiased spectral surveys at 0.8, 1, 2 and 3 mm have been obtained with the JCMT and IRAM 30-m telescopes. In order to investigate the morphology of this region, we used the IRAM Plateau de Bure Interferometer to image OMC-2 FIR 4 in the 2-mm continuum emission, as well as in DCO+(2-1), DCN(2-1), C34S(3-2), and several CH3OH lines. In addition, we analysed observations of the NH3(1,1) and (2,2) inversion transitions made with the Very Large Array of the NRAO. The resulting maps have an angular resolution which allows us to resolve structures of 5", equivalent to 2000 AU. Our observations reveal three spatially resolved sources within OMC-2 FIR 4, of one or several solar masses each, with hints of further unresolved substructure w...

  5. High-mass twins & resolution of the reconfinement, masquerade and hyperon puzzles of compact star interiors

    Energy Technology Data Exchange (ETDEWEB)

    Blaschke, David [Bogoliubov Laboratory for Theoretical Physics, JINR Dubna, 141980 Dubna (Russian Federation); Instytut Fizyki Teoretycznej, Uniwersytet Wroclawski, 50-204 Wroclaw (Poland); Alvarez-Castillo, David E. [Bogoliubov Laboratory for Theoretical Physics, JINR Dubna, 141980 Dubna (Russian Federation); Instituto de Física, Universidad Autónoma de San Luis Potosí, San Luis Potosí, México (Mexico)

    2016-01-22

    We aim at contributing to the resolution of three of the fundamental puzzles related to the still unsolved problem of the structure of the dense core of compact stars (CS): (i) the hyperon puzzle: how to reconcile pulsar masses of 2 M{sub ⊙} with the hyperon softening of the equation of state (EoS); (ii) the masquerade problem: modern EoS for cold, high density hadronic and quark matter are almost identical; and (iii) the reconfinement puzzle: what to do when after a deconfinement transition the hadronic EoS becomes favorable again? We show that taking into account the compositeness of baryons (by excluded volume and/or quark Pauli blocking) on the hadronic side and confining and stiffening effects on the quark matter side results in an early phase transition to quark matter with sufficient stiffening at high densities which removes all three present-day puzzles of CS interiors. Moreover, in this new class of EoS for hybrid CS falls the interesting case of a strong first order phase transition which results in the observable high mass twin star phenomenon, an astrophysical observation of a critical endpoint in the QCD phase diagram.

  6. De Novo Peptide Sequencing: Deep Mining of High-Resolution Mass Spectrometry Data.

    Science.gov (United States)

    Islam, Mohammad Tawhidul; Mohamedali, Abidali; Fernandes, Criselda Santan; Baker, Mark S; Ranganathan, Shoba

    2017-01-01

    High resolution mass spectrometry has revolutionized proteomics over the past decade, resulting in tremendous amounts of data in the form of mass spectra, being generated in a relatively short span of time. The mining of this spectral data for analysis and interpretation though has lagged behind such that potentially valuable data is being overlooked because it does not fit into the mold of traditional database searching methodologies. Although the analysis of spectra by de novo sequences removes such biases and has been available for a long period of time, its uptake has been slow or almost nonexistent within the scientific community. In this chapter, we propose a methodology to integrate de novo peptide sequencing using three commonly available software solutions in tandem, complemented by homology searching, and manual validation of spectra. This simplified method would allow greater use of de novo sequencing approaches and potentially greatly increase proteome coverage leading to the unearthing of valuable insights into protein biology, especially of organisms whose genomes have been recently sequenced or are poorly annotated.

  7. High Resolution, Long - Slit Spectroscopy of VY CMa: The Evidence for Localized High Mass Loss Events

    CERN Document Server

    Humphreys, R M; Ruch, G; Wallerstein, G; Humphreys, Roberta M.; Davidson, Kris; Ruch, Gerald; Wallerstein, George

    2004-01-01

    High spatial and spectral resolution spectroscopy of the OH/IR supergiant VY CMa and its circumstellar ejecta reveals evidence for high mass loss events from localized regions on the star occurring over the past 1000 years. The reflected absorption lines and the extremely strong K I emission lines show a complex pattern of velocities in the ejecta. We show that the large, dusty NW arc, expanding at 50 km/sec with respect to the embedded star, is kinematically distinct from the surrounding nebulosity and was ejected about 400 years ago. Other large, more filamentary loops were probably expelled as much as 800 to 1000 years ago while knots and small arcs close to the star resulted from more recent events 100 to 200 years ago. The more diffuse, uniformly distributed gas and dust is surprisingly stationary with little or no velocity relative to the star. This is not what we would expect for the circumstellar material from an evolved red supergiant with a long history of mass loss. We therefore suggest that the hi...

  8. Molecular characterization of effluent organic matter identified by ultrahigh resolution mass spectrometry.

    Science.gov (United States)

    Gonsior, Michael; Zwartjes, Matthew; Cooper, William J; Song, Weihua; Ishida, Kenneth P; Tseng, Linda Y; Jeung, Matthew K; Rosso, Diego; Hertkorn, Norbert; Schmitt-Kopplin, Philippe

    2011-04-01

    Effluent dissolved organic matter (EfOM) collected from the secondary-treated wastewater of the Orange County Sanitation District (OCSD) located in Fountain Valley, California, USA was compared to natural organic matter collected from the Suwannee River (SRNOM), Florida using ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Furthermore, the two different treatment processes at OCSD, activated sludge and trickling filter, were separately investigated. The blend of these two effluents was further evaluated after it had passed through the microfiltration process of the Advanced Water Purification Facility (AWPF) at Orange County Water District (OCWD). EfOM contained 872 different m/z peaks that were unambiguously assigned to exact molecular formulae containing a single sulfur atom and carbon, hydrogen and oxygen atoms (CHOS formulae). In contrast, the SRNOM sample only contained 152 CHOS formulae. The trend in CHO molecular compositions was opposite with 2500 CHO formulae assigned for SRNOM but only about 1000 for EfOM. The CHOS-derived mass peaks with highest abundances in EfOM could be attributed to surfactants such as linear alkyl benzene sulfonates (LAS), their co-products dialkyl tetralin sulfonates (DATS) and their biodegraded metabolites such as sulfophenyl carboxylic acids (SPC). The differences between the treatments were found minor with greater differences between sampling dates than treatment methods used.

  9. Characterization of unknown brominated disinfection byproducts during chlorination using ultrahigh resolution mass spectrometry.

    Science.gov (United States)

    Zhang, Haifeng; Zhang, Yahe; Shi, Quan; Zheng, Hongdie; Yang, Min

    2014-03-18

    Brominated disinfection byproducts (Br-DBPs), formed from the reaction of disinfectant(s) with natural organic matter in the presence of bromide in raw water, are generally more cytotoxic and genotoxic than their chlorinated analogues. To date, only a few Br-DBPs in drinking water have been identified, while a significant portion of Br-DBPs in drinking water is still unknown. In this study, negative ion electrospray ionization ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) was used to characterize unknown Br-DBPs in artificial drinking water. In total, 441 formulas for one-bromine-containing products and 37 formulas for two-bromine-containing products, most of which had not been previously reported, were detected in the chlorinated sample. Most Br-DBPs have corresponding chlorine-containing analogues with identical CHO composition. In addition, on-resonance collision-induced dissociation (CID) of single ultrahigh resolved bromine containing mass peaks was performed in the ICR cell to isolate single bromine-containing components in a very complex natural organic matter spectrum and provide structure information. Relatively abundant neutral loss of CO2 was observed in MS-MS spectra, indicating that the unknown Br-DBPs are rich in carboxyl groups. The results demonstrate that the ESI FT-ICR MS method could provide valuable molecular composition and structure information on unknown Br-DBPs.

  10. Analysis of bromotryptophan and hydroxyproline modifications by high-resolution, high-accuracy precursor ion scanning utilizing fragment ions with mass-deficient mass tags.

    Science.gov (United States)

    Steen, Hanno; Mann, Matthias

    2002-12-15

    Protein modifications are often detected by precursor ion scanning. When quadrupole TOF mass spectrometers are used for precursor ion scanning with high-resolution, high-accuracy fragment ion selection, "reporter" ions are required to have a unique mass within +/-0.04 Da or less instead of +/-0.5 Da on triple quadrupole mass spectrometers, the traditional instrument used for precursor ion scanning. Thus, characteristic fragment ions can be utilized even if other fragment ions have the same nominal mass as long as the characteristic fragment ions are slightly mass deficient as compared to the other fragments, i.e., when they have an inherent mass-deficient mass tag. Here, the immonium ions of bromotryptophan and hydroxyproline are described as two fragment ions characteristic for tryptophan-brominated and proline-hydroxylated peptides, respectively. The "reporter" ion of trytophan-brominated peptides is highly mass deficient due to the presence of bromine, thereby allowing the selective detection of these species and the distinction from other dipeptidic a-, b-, and y-fragment ions by high-resolution, high-accuracy precursor ion scanning. This strategy also enables the differentiation between precursors giving rise to the oxygen-containing immonium ion of hydroxyproline and precursors of the immonium ions of near-ubiquitous leucine/isoleucine. Both immonium ions have the same nominal mass of 86 Da, but the exact masses differ by less than 0.04 Da. High-resolution, high-accuracy precursor ion scanning enabled the identification of proline-hydroxylated and tryptophan-brominated species and the directed analysis of species carrying these modifications in a highly complex Conus textile conotoxin mixture. This lead to the characterization of one novel C. textile conotoxin containing a bromotryptophan residue and one novel C. textile conotoxin carrying two hydroxyproline residues.

  11. Advanced Characterization of Soil Organic Matter Using Ultra High Resolution Mass Spectrometry

    Science.gov (United States)

    Tfaily, M. M.; Chu, R.; Tolic, N.; Roscioli, K.; Robinson, E. R.; Paša-Tolić, L.; Hess, N. J.

    2014-12-01

    The focus on ecosystem stress and climate change is currently relevant as researchers and policymakers strive to understand the feedbacks between soil C dynamics and climate change. Successful development of molecular profiles that link soil microbiology with soil carbon (C) to ascertain soil vulnerability and resilience to climate change would have great impact on assessments of soil ecosystems in response to climate change. Additionally, better understanding of the dynamics of soil organic matter (SOM) plays a central role to climate modeling, and fate and transport of carbon. The use of ultra-high resolution mass spectrometry (UHR MS) has enabled the examination of molecules, directly from mixtures, with ultrahigh mass resolution and sub-ppm mass accuracy. In this study, EMSL's extensive expertise and capabilities in UHR MS proteomics were leveraged to develop extraction protocols for the characterization of carbon compounds in SOM, thereby providing the chemical and structural detail needed to develop mechanistic descriptions of soil carbon flow processes. Our experiments have allowed us to identify thousands of individual compounds in complex soil mixtures with a wide range of C content representing diverse ecosystems within the USA. The yield of the chemical extraction was dependent on (1) the type of solvent used and its polarity, (2) sample-to-solvent ratios and (3) the chemical and physical nature of the samples including their origins. Hexane, a non-polar organic solvent, was efficient in extracting lipid-like compounds regardless of soil origin or organic carbon %. For samples with high organic carbon %, acetonitrile extracted a wide range of compounds characterized with high O/C ratios, identified as polyphenolic compounds that were not observed with methanol extraction. Soils extracted with pyridine showed a similar molecular distribution to those extracted by methanol. Solvent extraction followed by UHR MS is a promising tool to understand the

  12. Use of Multicriteria Valuation of Spatial Units in a System of Mass Real Estate Valuation

    Directory of Open Access Journals (Sweden)

    Miroslav Kuburić

    2012-05-01

    Full Text Available A model of mass valuation at the national level must be functional, practically applicable, consistent and adaptable to actual conditions and real estate market trends. A consideration of the influence of location on real estate value in a spatial unit, and a description of spatial units with a sufficient number of attributes to determine a connection between the value of these attributes and the average price of real estate in a spatial unit, are important tasks in modelling a system of mass real estate valuation. This paper, based on a test implementation of mass real estate valuation for an area covering a number of municipalities in the Republic of Serbia, offers conclusions on the suitability of the use of a mass valuation method grounded in the principles of logical aggregation and case based reasoning. The values of location characteristics, or factors of spatial unit valuation, were determined in spatial analyses employing GIS, according to an established system of multicriteria valuation. This approach ensures that a model-defined value is not stored as offline data, but that each time such data is needed, it can be determined following the proposed methodology, based on actual, updated data from the databases of official spatial data registries. Prior to this, it is necessary to meet all the required prerequisites, which include the distributed databases of official real estate data registries and other factors needed in the mass valuation procedure. Keywords: real estate valuation; spatial units; multicriteria analysis

  13. Food contaminant analysis at ultra-high mass resolution: application of hybrid linear ion trap - orbitrap mass spectrometry for the determination of the polyether toxins, azaspiracids, in shellfish.

    LENUS (Irish Health Repository)

    2010-10-30

    The biotoxins, azaspiracids (AZAs), from marine phytoplankton accumulate in shellfish and affect human health by causing severe gastrointestinal disturbance, diarrhea, nausea and vomiting. Specific and sensitive methods have been developed and validated for the determination of the most commonly occurring azaspiracid analogs. An LTQ Orbitrap mass spectrometer is a hybrid instrument that combines linear ion trap (LIT) mass spectrometry (MS) with high-resolution Fourier transform (FT) MS and this was exploited to perform simultaneous ultra-high-resolution full-scan MS analysis and collision-induced dissociation (CID) tandem mass spectrometry (MS\\/MS). Using the highest mass resolution setting (100,000 FWHM) in full-scan mode, the methodology was validated for the determination of six AZAs in mussel (Mytilus galloprovincialis) tissue extracts. Ultra-high mass resolution, together with a narrow mass tolerance window of ±2 mDa, dramatically improved detection sensitivity. In addition to employing chromatographic resolution to distinguish between the isomeric azaspiracid analogs, AZA1\\/AZA6 and AZA4\\/AZA5, higher energy collisionally induced dissociation (HCD) fragmentation on selected precursor ions were performed in parallel with full-scan FTMS. Using HCD MS\\/MS, most precursor and product ion masses were determined within 1 ppm of the theoretical m\\/z values throughout the mass spectral range and this enhanced the reliability of analyte identity.For the analysis of mussels (M. galloprovincialis), the method limit of quantitation (LOQ) was 0.010 µg\\/g using full-scan FTMS and this was comparable with the LOQ (0.007 µg\\/g) using CID MS\\/MS. The repeatability data were; intra-day RSD% (1.8-4.4%; n = 6) and inter-day RSD% (4.7-8.6%; n = 3). Application of these methods to the analysis of mussels (M. edulis) that were naturally contaminated with azaspiracids, using high-resolution full-scan Orbitrap MS and low-resolution CID MS\\/MS, produced

  14. Identifying Spatial Units of Human Occupation in the Brazilian Amazon Using Landsat and CBERS Multi-Resolution Imagery

    Directory of Open Access Journals (Sweden)

    Maria Isabel Sobral Escada

    2012-01-01

    Full Text Available Every spatial unit of human occupation is part of a network structuring an extensive process of urbanization in the Amazon territory. Multi-resolution remote sensing data were used to identify and map human presence and activities in the Sustainable Forest District of Cuiabá-Santarém highway (BR-163, west of Pará, Brazil. The limits of spatial units of human occupation were mapped based on digital classification of Landsat-TM5 (Thematic Mapper 5 image (30m spatial resolution. High-spatial-resolution CBERS-HRC (China-Brazil Earth Resources Satellite-High-Resolution Camera images (5 m merged with CBERS-CCD (Charge Coupled Device images (20 m were used to map spatial arrangements inside each populated unit, describing intra-urban characteristics. Fieldwork data validated and refined the classification maps that supported the categorization of the units. A total of 133 spatial units were individualized, comprising population centers as municipal seats, villages and communities, and units of human activities, such as sawmills, farmhouses, landing strips, etc. From the high-resolution analysis, 32 population centers were grouped in four categories, described according to their level of urbanization and spatial organization as: structured, recent, established and dependent on connectivity. This multi-resolution approach provided spatial information about the urbanization process and organization of the territory. It may be extended into other areas or be further used to devise a monitoring system, contributing to the discussion of public policy priorities for sustainable development in the Amazon.

  15. High Spatial Resolution Time-of-Flight Secondary Ion Mass Spectrometry for the Masses: A Novel Orthogonal ToF FIB-SIMS Instrument with In Situ AFM

    Directory of Open Access Journals (Sweden)

    James A. Whitby

    2012-01-01

    Full Text Available We describe the design and performance of an orthogonal time-of-flight (TOF secondary ion mass spectrometer that can be retrofitted to existing focused ion beam (FIB instruments. In particular, a simple interface has been developed for FIB/SEM instruments from the manufacturer Tescan. Orthogonal extraction to the mass analyser obviates the need to pulse the primary ion beam and does not require the use of monoisotopic gallium to preserve mass resolution. The high-duty cycle and reasonable collection efficiency of the new instrument combined with the high spatial resolution of a gallium liquid metal ion source allow chemical observation of features smaller than 50 nm. We have also demonstrated the integration of a scanning probe microscope (SPM operated as an atomic force microscope (AFM within the FIB/SEM-SIMS chamber. This provides roughness information, and will also allow true three dimensional chemical images to be reconstructed from SIMS measurements.

  16. A 30m resolution hydrodynamic model of the entire conterminous United States.

    Science.gov (United States)

    Bates, P. D.; Neal, J. C.; Smith, A.; Sampson, C.; Johnson, K.; Wing, O.

    2016-12-01

    In this paper we describe the development and validation of a 30m resolution hydrodynamic model covering the entire conterminous United States. The model can be used to simulate inundation and water depths resulting from either return period flows (so equivalent to FEMA Flood Insurance Rate Maps), hindcasts of historic events or forecasts of future river flow from a rainfall-runoff or land surface model. As topographic data the model uses the U.S. Geological Survey National Elevation Dataset or NED, and return period flows are generated using a regional flood frequency analysis methodology (Smith et al., 2015. Worldwide flood frequency estimation. Water Resources Research, 51, 539-553). Flood defences nationwide are represented using data from the US Army Corps of Engineers. Using these data flows are simulated using an explicit and highly efficient finite difference solution of the local inertial form of the Shallow Water equations identical to that implemented in the LISFLOOD-FP model. Even with this efficient numerical solution a simulation at this resolution over a whole continent is a huge undertaking, and a variety of High Performance Computing technologies therefore need to be employed to make these simulations possible. The size of the output datasets is also challenging, and to solve this we use the GIS and graphical display functions of Google Earth Engine to facilitate easy visualisation and interrogation of the results. The model is validated against the return period flood extents contained in FEMA Flood Insurance Rate Maps and real flood event data from the Texas 2015 flood event which was hindcast using the model. Finally, we present an application of the model to the Upper Mississippi river basin where simulations both with and without flood defences are used to determine floodplain areas benefitting from protection in order to quantify the benefits of flood defence spending.

  17. Environmental forensics in groundwater coupling passive sampling and high resolution mass spectrometry for screening.

    Science.gov (United States)

    Soulier, Coralie; Coureau, Charlotte; Togola, Anne

    2016-09-01

    One of the difficulties encountered when monitoring groundwater quality is low and fluctuating concentration levels and complex mixtures of micropollutants, including emerging substances or transformation products. Combining passive sampling techniques with analysis by high resolution mass spectrometry (HRMS) should improve environmental metrology. Passive samplers accumulate compounds during exposure, which improves the detection of organic compounds and integrates pollution fluctuations. The Polar Organic Chemical Integrative Sampler (POCIS) were used in this study to sequester polar to semi-polar compounds. The methodology described here improves our knowledge of environmental pollution by highlighting and identifying pertinent compounds to be monitored in groundwater. The advantage of combining these two approaches is demonstrated on two different sites impacted by agricultural and/or urban pollution sources where groundwater was sampled for several months. Grab and passive sampling were done and analyzed by liquid chromatography coupled to a hybrid quadrupole time-of-flight mass spectrometer (LC-QTOF). Various data processing approaches were used (target, suspect and non-target screening). Target screening was based on research from compounds listed in a homemade database and suspect screening used a database compiled using literature data. The non-target screening was done using statistical tools such as principal components analysis (PCA) with direct connections between original chromatograms and ion intensity. Trend plots were used to highlight relevant compounds for their identification. The advantage of using POCIS to improve screening of polar organic compounds was demonstrated. Compounds undetected in water samples were detected with these tools. The subsequent data processing identified sentinel molecules, molecular clusters as compounds never revealed in these sampling sites, and molecular fingerprints. Samples were compared and multidimensional

  18. Thin Layer Chromatography-Autography-High Resolution Mass Spectrometry Analysis: Accelerating the Identification of Acetylcholinesterase Inhibitors.

    Science.gov (United States)

    Ramallo, I Ayelen; Salazar, Mario O; Furlan, Ricardo L E

    2015-01-01

    The prevailing treatment for Alzheimer's disease is the use of acetylcholinesterase (AChE) inhibitors. Natural extracts are the principal source of AChE's inhibitors. However, their chemical complexity demands for simple, selective and rapid assays. To develop a strategy for identification of AChE inhibitors present in mixtures employing high resolution mass spectrometry (HRMS) and thin layer chromatography (TLC)-biological staining. The strategy uses an autographic assay based on the α-naphthyl acetate - fast blue B system for the detection of AChE activity. The immobilisation of AChE in agar allowed the extraction of the compounds for analysis by HRMS. Three TLC experiments employing different solvent systems were used in parallel and the mass spectra of the compounds extracted from the inhibition halos, were compared. The analysis was performed under MatLab environment. The strategy was used to detect the presence of physostigmine in an extract of Brassica rapa L. spiked with the inhibitor. Similarly, caffeine was straightforwardly spotted as responsible for the inhibitory properties of an extract of Ilex paraguariensis Saint-Hilaire. Comparison of the HRMS profiles lead to the facile identification of the [M+H](+) and [M+Na](+) of the compounds responsible for the inhibition. The proposed methodology, coupling TLC-AChE autography-HRMS, illustrates the feasibility of assigning molecular formulas of active compounds present in complex mixtures directly from autography. The new AChE agar-immobilised assay presented a more homogenous colour and a better definition than direct spraying methods, reducing the cost of the assay and improving its sensitivity. Copyright © 2015 John Wiley & Sons, Ltd.

  19. Comprehensive Characterization of Atmospheric Organic Carbon using Multiple High-Resolution Mass Spectrometric Instruments

    Science.gov (United States)

    Kroll, J. H.; Hunter, J. F.; Isaacman-VanWertz, G. A.

    2015-12-01

    Accurate modeling of major atmospheric chemical processes (oxidant cycling, aerosol formation, etc.) requires understanding the identity, chemistry, and lifecycle (emission, reaction, and deposition) of atmospheric organic species. Such an understanding is generally limited by the wide diversity in chemical structure, properties, and reactivity of atmospheric organics, posing major challenges in detection and quantification. However the last several years have seen the development of several new techniques for the measurement of a wide range of carbon-containing compounds, including low-volatility, oxidized species that have traditionally been difficult to measure. Many of these new techniques are based on high-resolution mass spectrometry, enabling the unambiguous identification of individual ions, and hence the elemental ratios and carbon oxidation state of the organic species; most also provide information on volatility and/or carbon number distributions of the molecular species. While a single instrument can generally measure only species of a particular class (occupying a localized region of "chemical space"), here we show that the combined measurements from multiple instruments can provide a comprehensive picture of the chemical composition of the entire organic mixture. From these combined measurements, the organic species can be described not only in terms of organic carbon mass but also in terms of distributions of key ensemble properties (such as oxidation state and volatility), and thus can be used to populate and constrain the various reduced-dimensionality chemical spaces that have been put forth as frameworks for describing atmospheric organic chemistry. We apply this general measurement approach both to field data, providing information on ambient organic species, and to laboratory (chamber) studies, providing insight into the chemical transformations that organic species undergo upon atmospheric oxidation.

  20. Evaluation of Rock Mass Responses Using High Resolution Water-level Tiltmeter Arrays

    Science.gov (United States)

    Roberts, J. S.; Wang, H. F.; Fratta, D.; Stetler, L. D.; Volk, J. T.; Geox^Tm

    2010-12-01

    External forces act on the surface of the earth and produce deformation across all spatial and temporal scales. This research study focuses on the deformation evaluation of the rock-mass subjected to tidal, earthquake and surface forces. The events are monitored over horizontal distances of over 100 meters with tilt measurement arrays with a resolution of 10-8 radians. These measurements are obtained from hydrostatic leveling system (HLS) arrays that have been installed in the LaFarge mine in North Aurora, IL by Fermilab. Each sensor in the array is equipped with a water-filled reservoir beneath a capacitor. The amount of water in the reservoir is calculated as a function of the measured capacitance. Individual sensors are connected in a closed system via a water and air line. As the host rock expands and contracts sensors are raised relative to another and water is displaced. The water level in each reservoir is sent to a computer in the mine and recorded. In order to measure the tilt of the rock between two points, the difference in water levels between adjacent sensors is computed. The difference between the end sensors is also calculated to determine the larger-scale tilt of the array. The tiltmeters in LaFarge mine are supported by concrete pedestals installed on the floor of the drift. In the Homestake mine the tiltmeters are placed on similar pedestals, as well as platforms made of artificial wood decking. These platforms are fixed to the wall of the drift with a rock bolt. Time and frequency domain analyses were performed on time series ranging from hours to six months to capture relevant time scales including the response to the 2010 Chile Earthquake (hour-long scale), the stages of the moon (month scale), Fox River floods (flooding week long scales and pressure dissipation month-long scales). By monitoring tiltmeter array responses to different forces, we aim at making predictions about the material properties of rock masses.

  1. Characterization of Fumonisin A-Series by High-Resolution Liquid Chromatography-Orbitrap Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Masayoshi Tamura

    2014-08-01

    Full Text Available Fumonisin A-series (FAs in a reference material of corn sample that was naturally contaminated with fumonisins was characterized using high-resolution liquid chromatography-Orbitrap mass spectrometry (LC-Orbitap MS. Peaks for fumonisin B1 (FB1, fumonisin B2 (FB2, and fumonisin B3 (FB3, in addition to three peaks corresponding to unknown compounds I, II, and III, were detected in the chromatogram for the corn sample. Fragment ion analysis for FB1, FB2, and FB3 showed that while the ions formed at m/z values of 200–800 were similar to those formed by the cleavage of the tricarballylic acids and the hydroxyl groups, the fragmentation patterns at m/z values of 50–200 varied depending on the hydroxyl group locations in the compounds. Fragment ion analysis of compounds I–III revealed structural similarities to FBs, only differing by an additional C2H2O in the unknown compounds. Using these results and by comparing the product ion mass spectra of compound I with fumonisin A1 (FA1 synthesized from FB1 standards, compounds I–III were hypothesized to be N-acetyl analogs of FBs: fumonisins A1 (FA1, A2 (FA2, and A3 (FA3. The method for determining concentrations was validated with FA1, FB1, FB2, and FB3 standards and applied to analyze the reference material. The FB1, FB2, and FB3 analytical levels were within acceptance limits and the amount of FA1 in the material was ~15% of FB1 amount at 4.2 mg/kg.

  2. Rapid High-throughput Species Identification of Botanical Material Using Direct Analysis in Real Time High Resolution Mass Spectrometry.

    Science.gov (United States)

    Lesiak, Ashton D; Musah, Rabi A

    2016-10-02

    We demonstrate that direct analysis in real time-high resolution mass spectrometry can be used to produce mass spectral profiles of botanical material, and that these chemical fingerprints can be used for plant species identification. The mass spectral data can be acquired rapidly and in a high throughput manner without the need for sample extraction, derivatization or pH adjustment steps. The use of this technique bypasses challenges presented by more conventional techniques including lengthy chromatography analysis times and resource intensive methods. The high throughput capabilities of the direct analysis in real time-high resolution mass spectrometry protocol, coupled with multivariate statistical analysis processing of the data, provide not only class characterization of plants, but also yield species and varietal information. Here, the technique is demonstrated with two psychoactive plant products, Mitragyna speciosa (Kratom) and Datura (Jimsonweed), which were subjected to direct analysis in real time-high resolution mass spectrometry followed by statistical analysis processing of the mass spectral data. The application of these tools in tandem enabled the plant materials to be rapidly identified at the level of variety and species.

  3. Rapid High-throughput Species Identification of Botanical Material Using Direct Analysis in Real Time High Resolution Mass Spectrometry

    Science.gov (United States)

    Lesiak, Ashton D.; Musah, Rabi A.

    2016-01-01

    We demonstrate that direct analysis in real time-high resolution mass spectrometry can be used to produce mass spectral profiles of botanical material, and that these chemical fingerprints can be used for plant species identification. The mass spectral data can be acquired rapidly and in a high throughput manner without the need for sample extraction, derivatization or pH adjustment steps. The use of this technique bypasses challenges presented by more conventional techniques including lengthy chromatography analysis times and resource intensive methods. The high throughput capabilities of the direct analysis in real time-high resolution mass spectrometry protocol, coupled with multivariate statistical analysis processing of the data, provide not only class characterization of plants, but also yield species and varietal information. Here, the technique is demonstrated with two psychoactive plant products, Mitragyna speciosa (Kratom) and Datura (Jimsonweed), which were subjected to direct analysis in real time-high resolution mass spectrometry followed by statistical analysis processing of the mass spectral data. The application of these tools in tandem enabled the plant materials to be rapidly identified at the level of variety and species. PMID:27768072

  4. Enlightening the Mechanism of Copper Mediated PhotoRDRP via High-Resolution Mass Spectrometry.

    Science.gov (United States)

    Frick, Elena; Anastasaki, Athina; Haddleton, David M; Barner-Kowollik, Christopher

    2015-06-03

    The initiation mechanism of photochemically mediated Cu-based reversible-deactivation radical polymerization (photoRDRP) was investigated using pulsed-laser polymerization (PLP) and high-resolution mass spectrometry. The variation of the catalyst composition and ESI-MS analysis of the resulting products provided information on how initiator, ligand, copper species, and monomer are interacting upon irradiation with UV light. A discussion of the results allows for a new postulation of the mechanism of photoRDRP and-for the first time-the unambiguous identification of the initiating species and their interactions within the reaction mixture. One pathway for radical generation proceeds via UV light-induced C-Br bond scission of the initiator, giving rise to propagating radicals. The generation of copper(I) species from copper(II) can occur via several pathways, including, among others, via reduction by free amine ligand in its excited as well as from its ground state via the irradiation with UV light. The amine ligand serves as a strong reducing agent and is likely the main participant in the generation of copper(I) species.

  5. High-mass twins & resolution of the reconfinement, masquerade and hyperon puzzles of compact star interiors

    CERN Document Server

    Blaschke, David

    2016-01-01

    We aim at contributing to the resolution of three of the fundamental puzzles related to the still unsolved problem of the structure of the dense core of compact stars (CS): (i) the hyperon puzzle: how to reconcile pulsar masses of $2\\,$M$_\\odot$ with the hyperon softening of the equation of state (EoS); (ii) the masquerade problem: modern EoS for cold, high density hadronic and quark matter are almost identical; and (iii) the reconfinement puzzle: what to do when after a deconfinement transition the hadronic EoS becomes favorable again? We show that taking into account the compositeness of baryons (by excluded volume and/or quark Pauli blocking) on the hadronic side and confining and stiffening effects on the quark matter side results in an early phase transition to quark matter with sufficient stiffening at high densities which removes all three present-day puzzles of CS interiors. Moreover, in this new class of EoS for hybrid CS falls the interesting case of a strong first order phase transition which resul...

  6. Protein profile of exhaled breath condensate determined by high resolution mass spectrometry.

    Science.gov (United States)

    Muccilli, Vera; Saletti, Rosaria; Cunsolo, Vincenzo; Ho, Jenny; Gili, Elisa; Conte, Enrico; Sichili, Stefania; Vancheri, Carlo; Foti, Salvatore

    2015-02-01

    A method based on liquid chromatography/high resolution tandem mass spectrometry coupled with electrophoretic separation, for determination and relative quantification of the protein composition of exhaled breath condensate (EBC), was developed. Application of the procedure to a sample of EBC, pooled from nine healthy subjects, resulted in the identification of 167 unique gene products, 113 of which not previously reported in EBC samples. The abundance of the protein identified was estimated by means of the exponentially modified protein abundance index protocol (emPAI). Cytokeratins were by far the most abundant proteins in EBC samples. Many of the identified proteins were associated with multiple cellular location with cytoplasm constituting the largest group. Cytosol, nucleus, membrane, cytoskeleton and extracellular were other abundantly represented locations. No amylase was detected, suggesting the absence of saliva protein contamination. The profile obtained represents the most comprehensive protein characterization of EBC so far reported and demonstrates that this approach provides a powerful tool for investigating the protein profile of EBC samples. Compared with analogous investigations, this study also shows that the protein profile of EBC is strongly affected by the sampling method adopted.

  7. Ultrafast High-Resolution Mass Spectrometric Finger Pore Imaging in Latent Finger Prints

    Science.gov (United States)

    Elsner, Christian; Abel, Bernd

    2014-11-01

    Latent finger prints (LFPs) are deposits of sweat components in ridge and groove patterns, left after human fingers contact with a surface. Being important targets in biometry and forensic investigations they contain more information than topological patterns. With laser desorption mass spectrometry imaging (LD-MSI) we record `three-dimensional' finger prints with additional chemical information as the third dimension. Here we show the potential of fast finger pore imaging (FPI) in latent finger prints employing LD-MSI without a classical matrix in a high- spatial resolution mode. Thin films of gold rapidly sputtered on top of the sample are used for desorption. FPI employing an optical image for rapid spatial orientation and guiding of the desorption laser enables the rapid analysis of individual finger pores, and the chemical composition of their excretions. With this approach we rapidly detect metabolites, drugs, and characteristic excretions from the inside of the human organism by a minimally-invasive strategy, and distinguish them from chemicals in contact with fingers without any labeling. The fast finger pore imaging, analysis, and screening approach opens the door for a vast number of novel applications in such different fields as forensics, doping and medication control, therapy, as well as rapid profiling of individuals.

  8. Screening new psychoactive substances in urban wastewater using high resolution mass spectrometry.

    Science.gov (United States)

    González-Mariño, Iria; Gracia-Lor, Emma; Bagnati, Renzo; Martins, Claudia P B; Zuccato, Ettore; Castiglioni, Sara

    2016-06-01

    Analysis of drug residues in urban wastewater could complement epidemiological studies in detecting the use of new psychoactive substances (NPS), a continuously changing group of drugs hard to monitor by classical methods. We initially selected 52 NPS potentially used in Italy based on seizure data and consumption alerts provided by the Antidrug Police Department and the National Early Warning System. Using a linear ion trap-Orbitrap high resolution mass spectrometer, we designed a suspect screening and a target method approach and compared them for the analysis of 24 h wastewater samples collected at the treatment plant influents of four Italian cities. This highlighted the main limitations of these two approaches, so we could propose requirements for future research. A library of MS/MS spectra of 16 synthetic cathinones and 19 synthetic cannabinoids, for which analytical standards were acquired, was built at different collision energies and is available on request. The stability of synthetic cannabinoids was studied in analytical standards and wastewater, identifying the best analytical conditions for future studies. To the best of our knowledge, these are the first stability data on NPS. Few suspects were identified in Italian wastewater samples, in accordance with recent epidemiological data reporting a very low prevalence of use of NPS in Italy. This study outlines an analytical approach for NPS identification and measurement in urban wastewater and for estimating their use in the population.

  9. Method Development for the Detection of Human Myostatin by High-Resolution and Targeted Mass Spectrometry.

    Science.gov (United States)

    Peiris, Hassendrini Nileishika; Ashman, Keith; Vaswani, Kanchan; Kvaskoff, David; Rice, Gregory Edward; Mitchell, Murray David

    2014-06-30

    Myostatin, a highly conserved secretory protein, negatively regulates muscle development, affecting both the proliferation and differentiation of muscle cells. Proteolytic processing of the myostatin precursor protein generates a myostatin pro-peptide and mature protein. Dimerization of the mature myostatin protein creates the active form of myostatin. Myostatin dimer activity can be inhibited by noncovalent binding of two monomeric myostatin pro-peptides. This ability for myostatin to self-regulate as well as the altered expression of myostatin in states of abnormal health (e.g., muscle wasting) support the need for specific detection of myostatin forms. Current protein detection methods (e.g., Western blot) rely greatly on antibodies and are semiquantitative at best. Tandem mass spectometry (as in this study) provides a highly specific method of detection, enabling the characterization of myostatin protein forms through the analysis of discrete peptides fragments. Utilizing the scheduled high-resolution multiple reaction monitoring paradigm (sMRM(HR); AB SCIEX 5600 TripleTOF) we identified the lower limit of quantitation (LLOQ) of both mature (DFGLDCDEHSTESR) and pro-peptide regions (ELIDQYDVQR) as 0.19 nmol/L. Furthermore, scheduled multiple reaction monitoring (sMRM; AB SCIEX QTRAP 5500) identified a LLOQ for a peptide of the pro-peptide region (LETAPNISK) as 0.16 nmol/L and a peptide of the mature region (EQIIYGK) as 0.25 nmol/L.

  10. High Spatial Resolution Imaging Mass Spectrometry of Human Optic Nerve Lipids and Proteins

    Science.gov (United States)

    Anderson, David M. G.; Spraggins, Jeffrey M.; Rose, Kristie L.; Schey, Kevin L.

    2015-06-01

    The human optic nerve carries signals from the retina to the visual cortex of the brain. Each optic nerve is comprised of approximately one million nerve fibers that are organized into bundles of 800-1200 fibers surrounded by connective tissue and supportive glial cells. Damage to the optic nerve contributes to a number of blinding diseases including: glaucoma, neuromyelitis optica, optic neuritis, and neurofibromatosis; however, the molecular mechanisms of optic nerve damage and death are incompletely understood. Herein we present high spatial resolution MALDI imaging mass spectrometry (IMS) analysis of lipids and proteins to define the molecular anatomy of the human optic nerve. The localization of a number of lipids was observed in discrete anatomical regions corresponding to myelinated and unmyelinated nerve regions as well as to supporting connective tissue, glial cells, and blood vessels. A protein fragment from vimentin, a known intermediate filament marker for astrocytes, was observed surrounding nerved fiber bundles in the lamina cribrosa region. S100B was also found in supporting glial cell regions in the prelaminar region, and the hemoglobin alpha subunit was observed in blood vessel areas. The molecular anatomy of the optic nerve defined by MALDI IMS provides a firm foundation to study biochemical changes in blinding human diseases.

  11. Environmental Chemistry Compound Identification Using High Resolution Mass Spectrometry Data Integrated to the EPA Chemistry Dashboard (EAS)

    Science.gov (United States)

    There is a growing need for rapid chemical screening and prioritization to inform regulatory decision-making on thousands of chemicals in the environment. We have previously used high-resolution mass spectrometry to examine household vacuum dust samples using liquid chromatograph...

  12. Fabrication of transistors on flexible substrates: from mass-printing to high-resolution alternative lithography strategies

    NARCIS (Netherlands)

    Moonen, P.; Yakimets, I.; Huskens, J.

    2012-01-01

    In this report, the development of conventional, mass-printing strategies into high-resolution, alternative patterning techniques is reviewed with the focus on large-area patterning of flexible thin-film transistors (TFTs) for display applications. In the first part, conventional and digital printin

  13. The EPA iCSS Chemistry Dashboard to Support Compound Identification Using High Resolution Mass Spectrometry Data (ACS Fall meeting)

    Science.gov (United States)

    Abstract: There is a growing need for rapid chemical screening and prioritization to inform regulatory decision-making on thousands of chemicals in the environment. We have previously used high-resolution mass spectrometry to examine household vacuum dust samples using liquid chr...

  14. Screening of plant toxins in food,feed and botanicals using full-scan high-resolution (Orbitrap) mass spectrometry

    NARCIS (Netherlands)

    Mol, J.G.J.; Dam, van R.C.J.; Zomer, P.; Mulder, P.P.J.

    2011-01-01

    A generic method based on LC with full-scan high-resolution (Orbitrap) mass spectrometry (MS) was systematically investigated for the simultaneous detection of a wide range of plant toxins in a variety of food and feed matrices. For a selection of 150 substances, representing various chemical classe

  15. Screening of plant toxins in food,feed and botanicals using full-scan high-resolution (Orbitrap) mass spectrometry

    NARCIS (Netherlands)

    Mol, J.G.J.; Dam, van R.C.J.; Zomer, P.; Mulder, P.P.J.

    2011-01-01

    A generic method based on LC with full-scan high-resolution (Orbitrap) mass spectrometry (MS) was systematically investigated for the simultaneous detection of a wide range of plant toxins in a variety of food and feed matrices. For a selection of 150 substances, representing various chemical classe

  16. The EPA iCSS Chemistry Dashboard to Support Compound Identification Using High Resolution Mass Spectrometry Data (ACS Fall meeting)

    Science.gov (United States)

    Abstract: There is a growing need for rapid chemical screening and prioritization to inform regulatory decision-making on thousands of chemicals in the environment. We have previously used high-resolution mass spectrometry to examine household vacuum dust samples using liquid chr...

  17. Environmental Chemistry Compound Identification Using High Resolution Mass Spectrometry Data Integrated to the EPA Chemistry Dashboard (EAS)

    Science.gov (United States)

    There is a growing need for rapid chemical screening and prioritization to inform regulatory decision-making on thousands of chemicals in the environment. We have previously used high-resolution mass spectrometry to examine household vacuum dust samples using liquid chromatograph...

  18. Targeted metabolite profile of food bioactive compounds by Orbitrap high resolution mass spectrometry: The 'FancyTiles' approach

    NARCIS (Netherlands)

    Troise, A.D.; Ferracane, R.; Palermo, M.; Fogliano, V.

    2014-01-01

    In this paper a new targeted metabolic profile approach using Orbitrap high resolution mass spectrometry was described. For each foodmatrix various classes of bioactive compounds and some specificmetabolites of interest were selected on the basis of the existing knowledge creating an easy-to-read fi

  19. Linking high resolution mass spectrometry data with exposure and toxicity forecasts to advance high-throughput environmental monitoring

    Science.gov (United States)

    There is a growing need in the field of exposure science for monitoring methods that rapidly screen environmental media for suspect contaminants. Measurement and analysis platforms, based on high resolution mass spectrometry (HRMS), now exist to meet this need. Here we describe r...

  20. Comprehensive multidimensional gas chromatography coupled to low resolution quadrupole mass spectrometry for the analysis of PCDDs, PCDFs and PCBs

    Energy Technology Data Exchange (ETDEWEB)

    Costa, J.P. [Universitat de Barcelona (Spain). Facultat de Quimica, Dept. de Quimica Analitica; Korytar, P.; Boer, J. de [Netherlands Institutes for Fisheries Research, Ijmuiden (Netherlands); Leonards, P. [Instituto Quimico de Sarria, Barcelona (Spain)

    2004-09-15

    Because of the high persistency and extreme toxicity of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) and so-called dioxin-like polychlorinated biphenyls (PCBs), their trace level determination is a topic of much interest. The typical concentrations of this compounds, sub-ng/kg, makes that they have to be clearly separated from other, less toxic, congeners present in the samples and from the matrix and the use of sensitive techniques is required for the quantification. The analyses of the compounds are usually done by high resolution gas chromatography coupled to high resolution mass spectrometry (HRGC-HRMS). Recently, alternative novel techniques have been developed which are improving the chromatographic separation, e.g. comprehensive multidimensional gas chromatography (GC x GC), for the analysis of the compounds. The aim of this work is to evaluate GC x GC coupled to a low resolution quadrupole mass spectrometer for the quantification of PCDDs, PCDFs and dioxin like PCBs.

  1. Practical considerations for the rapid screening for pesticides using ambient pressure desorption ionisation with high-resolution mass spectrometry.

    Science.gov (United States)

    Edison, S E; Lin, L A; Parrales, L

    2011-10-01

    A rapid screening method for pesticides has been developed to streamline the processing of produce entering the United States. Foam swabs were used to recover multi-class mixtures of 240, 140, 132 and 60 pesticides from the surfaces of apples, kiwis, peaches and tomatoes. The mixtures were selected to span a large range of chemical classes, polarities, solubilities and sizes to provide a broad look at how this technique will perform for a variety of analytes. The swabs were analysed using direct analysis in real-time (DART) ionisation coupled with a high-resolution Exactive Orbitrap™ mass spectrometer. This study expands the types of commodities analysed using this method and explores the feasibility of compositing multiple units of produce per batch to analyse a representative sample. It was established that whilst smooth-skinned produce, such as apples, maintained a high detection rate for the pesticide mixtures even when ten apples are swabbed with one foam disk, commodities with rougher surfaces, such as peaches, suffered a decrease in detection rate when ten peaches are swabbed with one foam disk. In order to maintain some consistency across the sample preparation process, a composite size of three units was selected. The varying topography of the commodities necessitated minor modifications to the method; for example, analysis of kiwi required that the hair on the surface be shaved prior to swabbing to achieve good recovery. Additionally, the effect of storage conditions on detection rate was analysed by spiking the surface of tomatoes at levels of 5 and 10 ng g(-1) for each pesticide, storing them under refrigeration and ambient conditions for 3 and 8 days, and then analysing the surface using this method. After 8 days of storage under both conditions more than 80% of the pesticides in the mixture were detected. Also, analysis of the multi-class mixtures was performed in both positive- and negative-ion mode and many classes were detected in both modes

  2. Galaxy S-Stars Exhibit Orbital Angular Momentum Quantization per Unit Mass

    Directory of Open Access Journals (Sweden)

    Potter F.

    2012-10-01

    Full Text Available The innermost stars of our Galaxy, called S-stars, are in Keplerian orbits. Quantum celestial mechanics (QCM predicts orbital angular momentum quantization per unit mass for each of them. I determine the quantization integers for the 27 well-measured S-stars and the total angular momentum of this nearly isolated QCM system within the Galactic bulge.

  3. The role of mass media in disease outbreak reporting in the United ...

    African Journals Online (AJOL)

    The role of mass media in disease outbreak reporting in the United Republic of ... with accurate epidemiological reports if correct information is to reach the public. The role of media in outbreak reporting is herein discussed in relation to the ...

  4. The Atomic Mass Unit, the Avogadro Constant, and the Mole: A Way to Understanding

    Science.gov (United States)

    Baranski, Andrzej

    2012-01-01

    Numerous articles have been published that address problems encountered in teaching basic concepts of chemistry such as the atomic mass unit, Avogadro's number, and the mole. The origin of these problems is found in the concept definitions. If these definitions are adjusted for teaching purposes, understanding could be improved. In the present…

  5. A high-throughput de novo sequencing approach for shotgun proteomics using high-resolution tandem mass spectrometry

    Directory of Open Access Journals (Sweden)

    Banfield Jillian F

    2010-03-01

    Full Text Available Abstract Background High-resolution tandem mass spectra can now be readily acquired with hybrid instruments, such as LTQ-Orbitrap and LTQ-FT, in high-throughput shotgun proteomics workflows. The improved spectral quality enables more accurate de novo sequencing for identification of post-translational modifications and amino acid polymorphisms. Results In this study, a new de novo sequencing algorithm, called Vonode, has been developed specifically for analysis of such high-resolution tandem mass spectra. To fully exploit the high mass accuracy of these spectra, a unique scoring system is proposed to evaluate sequence tags based primarily on mass accuracy information of fragment ions. Consensus sequence tags were inferred for 11,422 spectra with an average peptide length of 5.5 residues from a total of 40,297 input spectra acquired in a 24-hour proteomics measurement of Rhodopseudomonas palustris. The accuracy of inferred consensus sequence tags was 84%. According to our comparison, the performance of Vonode was shown to be superior to the PepNovo v2.0 algorithm, in terms of the number of de novo sequenced spectra and the sequencing accuracy. Conclusions Here, we improved de novo sequencing performance by developing a new algorithm specifically for high-resolution tandem mass spectral data. The Vonode algorithm is freely available for download at http://compbio.ornl.gov/Vonode.

  6. Effects of Model Resolution and Subgrid-Scale Physics on the Simulation of Daily Precipitation in the Continental United States

    Energy Technology Data Exchange (ETDEWEB)

    Duffy, P B; Iorio, J P; Govindasamy, B; Thompson, S L; Khairoutdinov, M; Randall, D

    2004-07-28

    We analyze simulations of the global climate performed at a range of spatial resolutions to assess the effects of horizontal spatial resolution on the ability to simulate precipitation in the continental United States. The model investigated is the CCM3 general circulation model. We also preliminarily assess the effect of replacing cloud and convective parameterizations in a coarse-resolution (T42) model with an embedded cloud-system resolving model (CSRM). We examine both spatial patterns of seasonal-mean precipitation and daily-timescale temporal variability of precipitation in the continental United States. For DJF and SON, high-resolution simulations produce spatial patterns of seasonal-mean precipitation that agree more closely with observed precipitation patterns than do results from the same model (CCM3) at coarse resolution. However, in JJA and MAM, there is little improvement in spatial patterns of seasonal-mean precipitation with increasing resolution, particularly in the Southeast. This is owed to the dominance of convective (i.e., parameterized) precipitation in these two seasons. We further find that higher-resolution simulations have more realistic daily precipitation statistics. In particular, the well-known tendency at coarse resolution to have too many days with weak precipitation and not enough intense precipitation is partially eliminated in higher-resolution simulations. However, even at the highest resolution examined here (T239), the simulated intensity of the mean and of high-percentile daily precipitation amounts is too low. This is especially true in the Southeast, where the most extreme events occur. A new GCM, in which a cloud-resolving model (CSRM) is embedded in each grid cell and replaces convective and stratiform cloud parameterizations, solves this problem, and actually produces too much precipitation in the form of extreme events. However, in contrast to high-resolution versions of CCM3, this model produces little improvement in

  7. High-resolution field desorption/ionization fourier transform ion cyclotron resonance mass analysis of nonpolar molecules.

    Science.gov (United States)

    Schaub, Tanner M; Hendrickson, Christopher L; Qian, Kuangnan; Quinn, John P; Marshall, Alan G

    2003-05-01

    We report the first field desorption ionization broadband high-resolution (m/Deltam(50%) approximately 65 000) mass spectra. We have interfaced a field ionization/field desorption source to a home-built 9.4-T FT-ICR mass spectrometer. The instrumental configuration employs convenient sample introduction (in-source liquid injection) and external ion accumulation. We demonstrate the utility of this configuration by generating high-resolution positive-ion mass spectra of C(60) and a midboiling crude oil distillate. The latter contains species not accessible by common soft-ionization methods, for example, low-voltage electron ionization, electrospray ionization, and matrix-assisted laser desorption/ionization. The present work demonstrates significant advantages of FI/FD FT-ICR MS for analysis of nonpolar molecules in complex mixtures.

  8. Expanding the linear dynamic range for quantitative liquid chromatography-high resolution mass spectrometry utilizing natural isotopologue signals

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Hanghui, E-mail: Hanghui.Liu@senomyx.com [Senomyx Inc. 4767 Nexus Centre Dr., San Diego, CA 92121 (United States); Lam, Lily; Yan, Lin; Chi, Bert [Senomyx Inc. 4767 Nexus Centre Dr., San Diego, CA 92121 (United States); Dasgupta, Purnendu K., E-mail: Dasgupta@uta.edu [Department of Chemistry and Biochemistry, The University of Texas at Arlington, Arlington, TX 76019-0065 (United States)

    2014-11-19

    Highlights: • Less abundant isotopologue ions were utilized to decrease detector saturation. • A 25–50 fold increase in the upper limit of dynamic range was demonstrated. • Linear dynamic range was expanded without compromising mass resolution. - Abstract: The linear dynamic range (LDR) for quantitative liquid chromatography–mass spectrometry can be extended until ionization saturation is reached by using a number of target isotopologue ions in addition to the normally used target ion that provides the highest sensitivity. Less abundant isotopologue ions extend the LDR: the lower ion abundance decreases the probability of ion detector saturation. Effectively the sensitivity decreases and the upper limit of the LDR increases. We show in this paper that the technique is particularly powerful with a high resolution time of flight mass spectrometer because the data for all ions are automatically acquired, and we demonstrated this for four small organic molecules; the upper limits of LDRs increased by 25–50 times.

  9. An update of combined measurements of the new Higgs-like boson with high mass resolution channels

    CERN Document Server

    The ATLAS collaboration

    2012-01-01

    An update is presented of the measurement of the newly discovered boson properties using the high mass resolution channels, $H\\rightarrow\\,\\gamma\\gamma$ and $H \\rightarrow ZZ^{(*)}\\rightarrow 4\\ell$, with up to 4.8 fb$^{-1}$ of $pp$ collision data at $\\sqrt{s}=7$ TeV and 13 fb$^{-1}$ at $\\sqrt{s}=8$ TeV. The combined mass measurement derived from the $H\\rightarrow\\,\\gamma\\gamma$ and $H \\rightarrow ZZ^{(*)}\\rightarrow 4\\ell$ channels is $m_H=125.2 \\pm 0.3\\,(stat)\\,\\, \\pm 0.6\\,(sys)$ GeV. The combination of all final states, including the recently updated low mass resolution channels $H\\rightarrow\\,WW^{(*)}{\\rightarrow\\,}\\ell\

  10. A Computational Drug Metabolite Detection Using the Stable Isotopic Mass-Shift Filtering with High Resolution Mass Spectrometry in Pioglitazone and Flurbiprofen

    Directory of Open Access Journals (Sweden)

    Yohei Miyamoto

    2013-09-01

    Full Text Available The identification of metabolites in drug discovery is important. At present, radioisotopes and mass spectrometry are both widely used. However, rapid and comprehensive identification is still laborious and difficult. In this study, we developed new analytical software and employed a stable isotope as a tool to identify drug metabolites using mass spectrometry. A deuterium-labeled compound and non-labeled compound were both metabolized in human liver microsomes and analyzed by liquid chromatography/time-of-flight mass spectrometry (LC-TOF-MS. We computationally aligned two different MS data sets and filtered ions having a specific mass-shift equal to masses of labeled isotopes between those data using our own software. For pioglitazone and flurbiprofen, eight and four metabolites, respectively, were identified with calculations of mass and formulas and chemical structural fragmentation analysis. With high resolution MS, the approach became more accurate. The approach detected two unexpected metabolites in pioglitazone, i.e., the hydroxypropanamide form and the aldehyde hydrolysis form, which other approaches such as metabolite-biotransformation list matching and mass defect filtering could not detect. We demonstrated that the approach using computational alignment and stable isotopic mass-shift filtering has the ability to identify drug metabolites and is useful in drug discovery.

  11. The minimum mass of detectable planets in protoplanetary discs and the derivation of planetary masses from high resolution observations

    CERN Document Server

    Rosotti, Giovanni P; Booth, Richard A; Clarke, Cathie J

    2016-01-01

    We investigate the minimum planet mass that produces observable signatures in infrared scattered light and submm continuum images and demonstrate how these images can be used to measure planet masses to within a factor of about two. To this end we perform multi-fluid gas and dust simulations of discs containing low mass planets, generating simulated observations at $1.65 \\mu$m, $10 \\mu$m and $850 \\mu$m. We show that the minimum planet mass that produces a detectable signature is $\\sim 15 M_\\oplus$: this value is strongly dependent on disc temperature and changes slightly with wavelength (favouring the submm). We also confirm previous results that there is a minimum planet mass of $\\sim 20 M_\\oplus$ that produces a pressure maximum in the disc: only planets above this threshold mass generate a dust trap that can eventually create a hole in the submm dust. Below this mass, planets produce annular enhancements in dust outward of the planet and a reduction in the vicinity of the planet. These features are in stea...

  12. The minimum mass of detectable planets in protoplanetary discs and the derivation of planetary masses from high-resolution observations

    Science.gov (United States)

    Rosotti, Giovanni P.; Juhasz, Attila; Booth, Richard A.; Clarke, Cathie J.

    2016-07-01

    We investigate the minimum planet mass that produces observable signatures in infrared scattered light and submillimetre (submm) continuum images and demonstrate how these images can be used to measure planet masses to within a factor of about 2. To this end, we perform multi-fluid gas and dust simulations of discs containing low-mass planets, generating simulated observations at 1.65, 10 and 850 μm. We show that the minimum planet mass that produces a detectable signature is ˜15 M⊕: this value is strongly dependent on disc temperature and changes slightly with wavelength (favouring the submm). We also confirm previous results that there is a minimum planet mass of ˜20 M⊕ that produces a pressure maximum in the disc: only planets above this threshold mass generate a dust trap that can eventually create a hole in the submm dust. Below this mass, planets produce annular enhancements in dust outwards of the planet and a reduction in the vicinity of the planet. These features are in steady state and can be understood in terms of variations in the dust radial velocity, imposed by the perturbed gas pressure radial profile, analogous to a traffic jam. We also show how planet masses can be derived from structure in scattered light and submm images. We emphasize that simulations with dust need to be run over thousands of planetary orbits so as to allow the gas profile to achieve a steady state and caution against the estimation of planet masses using gas-only simulations.

  13. The minimum mass of detectable planets in protoplanetary discs and the derivation of planetary masses from high-resolution observations.

    Science.gov (United States)

    Rosotti, Giovanni P; Juhasz, Attila; Booth, Richard A; Clarke, Cathie J

    2016-07-01

    We investigate the minimum planet mass that produces observable signatures in infrared scattered light and submillimetre (submm) continuum images and demonstrate how these images can be used to measure planet masses to within a factor of about 2. To this end, we perform multi-fluid gas and dust simulations of discs containing low-mass planets, generating simulated observations at 1.65, 10 and 850 μm. We show that the minimum planet mass that produces a detectable signature is ∼15 M⊕: this value is strongly dependent on disc temperature and changes slightly with wavelength (favouring the submm). We also confirm previous results that there is a minimum planet mass of ∼20 M⊕ that produces a pressure maximum in the disc: only planets above this threshold mass generate a dust trap that can eventually create a hole in the submm dust. Below this mass, planets produce annular enhancements in dust outwards of the planet and a reduction in the vicinity of the planet. These features are in steady state and can be understood in terms of variations in the dust radial velocity, imposed by the perturbed gas pressure radial profile, analogous to a traffic jam. We also show how planet masses can be derived from structure in scattered light and submm images. We emphasize that simulations with dust need to be run over thousands of planetary orbits so as to allow the gas profile to achieve a steady state and caution against the estimation of planet masses using gas-only simulations.

  14. The modelled surface mass balance of the Antarctic Peninsula at 5.5 km horizontal resolution

    Directory of Open Access Journals (Sweden)

    J. M. van Wessem

    2015-09-01

    Full Text Available This study presents a high-resolution (~ 5.5 km estimate of Surface Mass Balance (SMB over the period 1979–2014 for the Antarctic Peninsula (AP, generated by the regional atmospheric climate model RACMO2.3 and a Firn Densification Model (FDM. RACMO2.3 is used to force the FDM, which calculates processes in the snowpack, such as meltwater percolation, refreezing and runoff. We evaluate model output with 132 in-situ SMB observations and discharge rates from 6 glacier drainage basins, and find that the model realistically simulates the strong spatial variability in precipitation, but that significant biases remain as a result of the highly complex topography of the AP. It is also clear that the observations significantly underrepresent the high-accumulation regimes. The SMB map reveals large accumulation gradients, with precipitation values above 3000 mm we yr−1 over the western AP (WAP and below 500 mm we yr−1 on the eastern AP (EAP, not resolved by coarser data-sets such as ERA-Interim. The other SMB components are one order of magnitude smaller, with drifting snow sublimation the largest ablation term removing up to 100 mm we yr−1 of mass. Snowmelt is widespread over the AP, reaching 500 mm we yr−1 towards the northern ice shelves, but the meltwater mostly refreezes. As a result runoff fluxes are low, but still considerable (200 mm we yr−1 over the Larsen (B/C, Wilkins and George VI ice shelves. The average AP ice sheet integrated SMB, including ice shelves (an area of 4.1 × 105 km2, is estimated at 351 Gt yr−1 with an interannual variability of 58 Gt yr−1, which is dominated by precipitation (PR (365 ± 57 Gt yr−1. The WAP (2.4 × 105 km2 SMB (276 ± 47 Gt yr−1, where PR is large (276 ± 47 Gt yr−1, dominates over the EAP (1.7 × 105 km2 SMB (75 ± 11 Gt yr−1 and PR (84 ± 11 Gt yr−1. Total sublimation is 11 ± 2 Gt yr−1 and meltwater runoff into the ocean is 4 ± 4 Gt yr−1. There are no significant trends in any

  15. Aerosol Composition in the Los Angeles Basin Studied by High Resolution Aerosol Mass Spectrometry

    Science.gov (United States)

    Hayes, P. L.; Ortega, A. M.; Cubison, M.; Hu, W.; Toohey, D. W.; Flynn, J. H.; Grossberg, N.; Lefer, B. L.; Alvarez, S. L.; Rappenglueck, B.; Allan, J. D.; Taylor, J.; Holloway, J. S.; Gilman, J. B.; Kuster, W. C.; De Gouw, J. A.; Massoli, P.; Zhang, X.; Weber, R.; Zhao, Y.; Cliff, S. S.; Wexler, A. S.; Isaacman, G. A.; Worton, D. R.; Kreisberg, N. M.; Hering, S. V.; Goldstein, A. H.; Jimenez, J. L.

    2011-12-01

    Atmospheric aerosols impact climate and health, but their sources and composition are poorly understood. To address this knowledge gap, a high-resolution aerosol mass spectrometer (AMS) and complementary instrumentation were deployed during the 2010 CalNex campaign to characterize aerosol composition in the Los Angeles (LA) area. Total mass concentrations as well as the species concentrations measured by the AMS compare well with most other instruments. Nitrate dominates in the mornings, but its concentration is reduced in the afternoon when organic aerosols (OA) increase and dominate. The diurnal variations in concentrations are strongly influenced by emission transport from the source-rich western basin. The average OA to enhanced CO ratio increases with photochemical age from 25 to 80 μg m-3 ppm-1, which indicates significant secondary OA (SOA) production and that a large majority of OA is secondary in aged air. The ratio values are similar to those from Mexico City as well as New England and the Mid-Atlantic States. Positive matrix factorization (PMF) is used to assess the concentrations of different OA components. The major OA classes are oxygenated OA (OOA, a surrogate for total SOA), and hydrocarbon-like OA (HOA, a surrogate for primary combustion OA). Several subclasses of OA are identified as well including diesel-influenced HOA (DI-HOA) and non-diesel HOA. DI-HOA exhibits low concentrations on Sundays consistent with the well-known weekday/weekend effect in LA. PMF analysis finds that OOA is 67% of the total OA concentration. A strong correlation between OOA and Ox (O3 + NO2) concentrations is observed with a slope of 0.15 that suggests the production of fresh SOA in Pasadena. Plotting the OA elemental ratios in a Van Krevelen diagram (H:C vs. O:C) yields a slope of -0.6, which is less steep than that observed in Riverside during the SOAR-2005 campaign. The difference in slopes may be attributed to the highly oxidized HOA present in Pasadena that is

  16. Solar Mass Loss, the Astronomical Unit, and the Scale of the Solar System

    CERN Document Server

    Noerdlinger, Peter D

    2008-01-01

    The radiative and particulate loss of mass by the Sun, -9.13*10^-14 Solar masses per year or more causes the orbits of the planets to expand at the same rate, and their periods to lengthen at twice this rate. Unfortunately, under the present definition of the Astronomical Unit (AU) based on the fixed Gaussian gravity constant kGS = 0.01720209895 (AU)^1.5/day, the value AUmet of the AU in meters must decrease at 1/3 this rate, all these rates being expressed logarithmically. The progress of the planets along their orbits slows quadratically with time. For example, in one century Mercury would lag behind the position predicted using constant solar mass by almost 1.4 km, in two centuries 5.5 km. The value of AUmet can be made constant by redefining it, based on a reference solar mass unit, such as the solar mass at J2000; else, the solar Gaussian gravity constant kGS used in defining the AU could be redefined proportional to the square root of the solar mass. Improved accuracy of the ephemerides would impose use...

  17. Characterization of unknown iodinated disinfection byproducts during chlorination/chloramination using ultrahigh resolution mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xin; Wang, Juan [State Key Laboratory of Environmental Aquatic Chemistry, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085 (China); Zhang, Yahe; Shi, Quan [State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249 (China); Zhang, Haifeng; Zhang, Yu [State Key Laboratory of Environmental Aquatic Chemistry, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085 (China); Yang, Min, E-mail: yangmin@rcees.ac.cn [State Key Laboratory of Environmental Aquatic Chemistry, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085 (China)

    2016-06-01

    Iodinated disinfection byproducts (I-DBPs), formed from the reaction of disinfectant(s) with organic matter in the presence of iodide in raw water, have recently been focused because of their more cytotoxic and genotoxic properties than their chlorinated or brominated analogues. To date, only a few I-DBPs in drinking water have been identified. In this study, C18 solid phase extraction coupled with electrospray ionization ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) was used to characterize unknown I-DBPs in chloraminated/chlorinated water spiked with iodide and humic substances. In total, 178 formulas for one-iodine-containing products, 13 formulas for two-iodine-containing products, and 15 formulas for one-chlorine and one-iodine-containing products were detected in the chloraminated water sample, while only 9 formulas for one-iodine-containing products and 6 formulas for one-chlorine and one-iodine-containing products were found in the chlorinated water sample. Most I-DBPs have corresponding chlorine-containing analogues with identical CHO compositions. As indicated by the modified aromaticity index (AI{sub mod}), in the C18 extracts, more than 68% of the I-DBPs have aromatic structures or polycyclic aromatic structures. This result demonstrates that the use of chloramination as an alternative disinfection method may lead to the formation of abundant species of I-DBPs in the presence of iodide. Thus, the suitability of adopting chloramination as an alternative disinfection method should be reevaluated, particularly when iodide is present in raw water. - Highlights: • The formulas of 206 iodinated DBPs in chloraminated drinking water were proposed. • More than 68% of the I-DBPs might have aromatic or polycyclic aromatic structures. • Precursors with high aromaticity is preferential to form iodinated DBPs.

  18. High-resolution mass spectrometry driven discovery of peptidic danger signals in insect immunity.

    Science.gov (United States)

    Berisha, Arton; Mukherjee, Krishnendu; Vilcinskas, Andreas; Spengler, Bernhard; Römpp, Andreas

    2013-01-01

    The 'danger model' is an alternative concept for immune response postulating that the immune system reacts to entities that do damage (danger associated molecular patterns, DAMP) and not only to entities that are foreign (pathogen-associated molecular patterns, PAMP) as proposed by classical immunology concepts. In this study we used Galleria mellonella to validate the danger model in insects. Hemolymph of G. mellonella was digested with thermolysin (as a representative for virulence-associated metalloproteinases produced by humanpathogens) followed by chromatographic fractionation. Immune-stimulatory activity was tested by measuring lysozyme activity with the lytic zone assays against Micrococcus luteus cell wall components. Peptides were analyzed by nano-scale liquid chromatography coupled to high-resolution Fourier transform mass spectrometers. Addressing the lack of a genome sequence we complemented the rudimentary NCBI protein database with a recently established transcriptome and de novo sequencing methods for peptide identification. This approach led to identification of 127 peptides, 9 of which were identified in bioactive fractions. Detailed MS/MS experiments in comparison with synthetic analogues confirmed the amino acid sequence of all 9 peptides. To test the potential of these putative danger signals to induce immune responses we injected the synthetic analogues into G. mellonella and monitored the anti-bacterial activity against living Micrococcus luteus. Six out of 9 peptides identified in the bioactive fractions exhibited immune-stimulatory activity when injected. Hence, we provide evidence that small peptides resulting from thermolysin-mediated digestion of hemolymph proteins function as endogenous danger signals which can set the immune system into alarm. Consequently, our study indicates that the danger model also plays a role in insect immunity.

  19. The modelled surface mass balance of the Antarctic Peninsula at 5.5 km horizontal resolution

    Science.gov (United States)

    van Wessem, J. M.; Ligtenberg, S. R. M.; Reijmer, C. H.; van de Berg, W. J.; van den Broeke, M. R.; Barrand, N. E.; Thomas, E. R.; Turner, J.; Wuite, J.; Scambos, T. A.; van Meijgaard, E.

    2016-02-01

    This study presents a high-resolution (˜ 5.5 km) estimate of surface mass balance (SMB) over the period 1979-2014 for the Antarctic Peninsula (AP), generated by the regional atmospheric climate model RACMO2.3 and a firn densification model (FDM). RACMO2.3 is used to force the FDM, which calculates processes in the snowpack, such as meltwater percolation, refreezing and runoff. We evaluate model output with 132 in situ SMB observations and discharge rates from six glacier drainage basins, and find that the model realistically simulates the strong spatial variability in precipitation, but that significant biases remain as a result of the highly complex topography of the AP. It is also clear that the observations significantly underrepresent the high-accumulation regimes, complicating a full model evaluation. The SMB map reveals large accumulation gradients, with precipitation values above 3000 mm we yr-1 in the western AP (WAP) and below 500 mm we yr-1 in the eastern AP (EAP), not resolved by coarser data sets such as ERA-Interim. The average AP ice-sheet-integrated SMB, including ice shelves (an area of 4.1 × 105 km2), is estimated at 351 Gt yr-1 with an interannual variability of 58 Gt yr-1, which is dominated by precipitation (PR) (365 ± 57 Gt yr-1). The WAP (2.4 × 105 km2) SMB (276 ± 47 Gt yr-1), where PR is large (276 ± 47 Gt yr-1), dominates over the EAP (1.7 × 105 km2) SMB (75 ± 11 Gt yr-1) and PR (84 ± 11 Gt yr-1). Total sublimation is 11 ± 2 Gt yr-1 and meltwater runoff into the ocean is 4 ± 4 Gt yr-1. There are no significant trends in any of the modelled AP SMB components, except for snowmelt that shows a significant decrease over the last 36 years (-0.36 Gt yr-2).

  20. Signal Enhancement with Stacked Magnets for High-Resolution Radio Frequency Glow Discharge Mass Spectrometry.

    Science.gov (United States)

    Wei, Juan; Dong, Jiangli; Zhuo, Shangjun; Qian, Rong; Fang, Yuanxing; Chen, Qiao; Patel, Ekbal

    2017-01-17

    A method for signal enhancement utilizing stacked magnets was introduced into high-resolution radio frequency glow discharge-mass spectrometry (rf-GD-MS) for significantly improved analysis of inorganic materials. Compared to the block magnet, the stacked magnets method was able to achieve 50-59% signal enhancement for typical elements in Y2O3, BSO, and BTN samples. The results indicated that signal was enhanced as the increase of discharge pressure from 1.3 to 8.0 mPa, the increase of rf-power from 10 to 50 W with a frequency of 13.56 MHz, the decrease of sample thickness, and the increase of number of stacked magnets. The possible mechanism for the signal enhancement was further probed using the software "Mechanical APDL (ANSYS) 14.0". It was found that the distinct oscillated magnetic field distribution from the stacked magnets was responsible for signal enhancement, which could extend the movement trajectories of electrons and increase the collisions between the electrons and neutral particles to increase the ionization efficiency. Two NIST samples were used for the validation of the method, and the results suggested that relative errors were within 13% and detection limit for six transverse stacked magnets could reach as low as 0.0082 μg g(-1). Additionally, the stability of the method was also studied. RSD within 15% of the elements in three nonconducting samples could be obtained during the sputtering process. Together, the results showed that the signal enhancement method with stacked magnets could offer great promises in providing a sensitive, stable, and facile solution for analyzing the nonconducting materials.

  1. Characterization of unknown iodinated disinfection byproducts during chlorination/chloramination using ultrahigh resolution mass spectrometry.

    Science.gov (United States)

    Wang, Xin; Wang, Juan; Zhang, Yahe; Shi, Quan; Zhang, Haifeng; Zhang, Yu; Yang, Min

    2016-06-01

    Iodinated disinfection byproducts (I-DBPs), formed from the reaction of disinfectant(s) with organic matter in the presence of iodide in raw water, have recently been focused because of their more cytotoxic and genotoxic properties than their chlorinated or brominated analogues. To date, only a few I-DBPs in drinking water have been identified. In this study, C18 solid phase extraction coupled with electrospray ionization ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) was used to characterize unknown I-DBPs in chloraminated/chlorinated water spiked with iodide and humic substances. In total, 178 formulas for one-iodine-containing products, 13 formulas for two-iodine-containing products, and 15 formulas for one-chlorine and one-iodine-containing products were detected in the chloraminated water sample, while only 9 formulas for one-iodine-containing products and 6 formulas for one-chlorine and one-iodine-containing products were found in the chlorinated water sample. Most I-DBPs have corresponding chlorine-containing analogues with identical CHO compositions. As indicated by the modified aromaticity index (AImod), in the C18 extracts, more than 68% of the I-DBPs have aromatic structures or polycyclic aromatic structures. This result demonstrates that the use of chloramination as an alternative disinfection method may lead to the formation of abundant species of I-DBPs in the presence of iodide. Thus, the suitability of adopting chloramination as an alternative disinfection method should be reevaluated, particularly when iodide is present in raw water.

  2. USGS Small-scale Dataset - 100-Meter Resolution Satellite View with Shaded Relief of the Conterminous United States 201304 GeoTIFF

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — The Satellite View with Shaded Relief of the Conterminous United States map layer is a 100-meter resolution simulated natural-color image of the United States, with...

  3. High-resolution Orbitrap mass spectrometry for the analysis of carotenoids in tomato fruit: validation and comparative evaluation towards UV-VIS and tandem mass spectrometry.

    Science.gov (United States)

    Van Meulebroek, Lieven; Vanden Bussche, Julie; Steppe, Kathy; Vanhaecke, Lynn

    2014-04-01

    In this study, a generic extraction protocol and full-scan high-resolution Orbitrap-mass spectrometry (MS) detection method were developed, enabling the metabolomic screening for carotenoids in tomato fruit tissue. To this end, the carotenoids lutein, zeaxanthin, α-carotene, β-carotene, and lycopene (representing both xanthofylls and carotenes) were considered. The extraction procedure was optimized by means of a D-optimal design and consisted of a liquid-liquid extraction with methanol/tert-butyl methyl ether (1:1, v/v). The considered compounds were detected by a single-stage Exactive(TM) mass spectrometer, operating at a mass resolution of 100,000 full width at half maximum. The validation study demonstrated excellent performance in terms of linearity (R (2) > 0.99), repeatability (CV ≤ 10.6 %), within-laboratory reproducibility (CV ≤ 12.2 %), and mean corrected recovery (ranging from 85 to 106 %). Additionally, a comparative evaluation towards well-established detection techniques, i.e., tandem mass spectrometry (MS/MS) and ultraviolet-visible spectroscopy (UV-VIS) photodiode array, indicated superior performance of high-resolution Orbitrap-MS with regard to specificity/selectivity and sensitivity (with limits of detection ranging from 1.0 to 3.8 pg μL(-1)). As a result, it may be concluded that high-resolution Orbitrap-MS is a suited alternative for UV-VIS or MS/MS in analyzing carotenoids and may offer significant value in carotenoid research because of the metabolomic screening possibilities.

  4. Experimental study on mass transfer of contaminants through an enthalpy recovery unit with polymer membrane foils

    DEFF Research Database (Denmark)

    Nie, Jinzhe; Fang, Lei

    2014-01-01

    recovery unit with polymer membrane foils was used as refeering unit in this study. The experiments were conducted with different outdoor thermal climates e.g. warm-humid and cold-dry climates; isothermal and non isothermal as well as equal humidity and non equal humidity with indoor climate. Three......Laboratory experimental studies were conducted to investigate the mass transfer of contaminants through a total heat recovery unit with polymer membranes foils. The studies were conducted in twin climate chambers which simulated outdoor and indoor thermal climates. One manufacturd total heat...... chemical gases were used to simulate air contaminants. The concentrations of dosed contaminants in the supply and exhaust air upstream and downstream of the total heat recovery unit were measured with Multi-Gas Monitor Innova 1316 in real time. Experiment results showed that 5% to 9% of dosed contaminants...

  5. Introduction to Mass Unit kg%浅谈质量单位千克

    Institute of Scientific and Technical Information of China (English)

    黄爱军; 赵明泽

    2014-01-01

    Kilogram in the international unit system is the basic unit of mass, its symbol is kg, and it is equal to the mass of the international kilogram original device. The use of kilogram is increasingly frequent. Deeply and correctly understanding and using kilogram are benefit for people to have a more comprehensive understanding of the mass of the object, and play a more and more important role in ensuring unite, accurate and consistent of the mass value. This paper studies and reviews the origin and the development history of mass unit kg, laying a solid foundation for the future development of related research.%在国际单位制中千克是表示质量的基本单位,它的符号是kg,它等于国际千克原器的质量。千克的使用日渐频繁,深入地了解千克、正确地理解和使用千克对于人们对物体的质量有较全面的认识大有裨益,对于保证质量量值的统一、准确、一致的作用越来越大。本文研究和回顾了质量单位千克的由来和发展历史,为今后相关研究的开展打下了坚实基础。

  6. Development of high-spatial and high-mass resolution mass spectrometric imaging (MSI) and its application to the study of small metabolites and endogenous molecules of plants

    Energy Technology Data Exchange (ETDEWEB)

    Jun, Ji Hyun [Iowa State Univ., Ames, IA (United States)

    2012-01-01

    High-spatial and high-mass resolution laser desorption ionization (LDI) mass spectrometric (MS) imaging technology was developed for the attainment of MS images of higher quality containing more information on the relevant cellular and molecular biology in unprecedented depth. The distribution of plant metabolites is asymmetric throughout the cells and tissues, and therefore the increase in the spatial resolution was pursued to reveal the localization of plant metabolites at the cellular level by MS imaging. For achieving high-spatial resolution, the laser beam size was reduced by utilizing an optical fiber with small core diameter (25 μm) in a vacuum matrix-assisted laser desorption ionization-linear ion trap (vMALDI-LTQ) mass spectrometer. Matrix application was greatly improved using oscillating capillary nebulizer. As a result, single cell level spatial resolution of ~ 12 μm was achieved. MS imaging at this high spatial resolution was directly applied to a whole Arabidopsis flower and the substructures of an anther and single pollen grains at the stigma and anther were successfully visualized. MS imaging of high spatial resolution was also demonstrated to the secondary roots of Arabidopsis thaliana and a high degree of localization of detected metabolites was successfully unveiled. This was the first MS imaging on the root for molecular species. MS imaging with high mass resolution was also achieved by utilizing the LTQ-Orbitrap mass spectrometer for the direct identification of the surface metabolites on the Arabidopsis stem and root and differentiation of isobaric ions having the same nominal mass with no need of tandem mass spectrometry (MS/MS). MS imaging at high-spatial and high-mass resolution was also applied to cer1 mutant of the model system Arabidopsis thaliana to demonstrate its usefulness in biological studies and reveal associated metabolite changes in terms of spatial distribution and/or abundances compared to those of wild-type. The spatial

  7. Development of high-spatial and high-mass resolution mass spectrometric imaging (MSI) and its application to the study of small metabolites and endogenous molecules of plants

    Energy Technology Data Exchange (ETDEWEB)

    Jun, Ji Hyun [Iowa State Univ., Ames, IA (United States)

    2012-01-01

    High-spatial and high-mass resolution laser desorption ionization (LDI) mass spectrometric (MS) imaging technology was developed for the attainment of MS images of higher quality containing more information on the relevant cellular and molecular biology in unprecedented depth. The distribution of plant metabolites is asymmetric throughout the cells and tissues, and therefore the increase in the spatial resolution was pursued to reveal the localization of plant metabolites at the cellular level by MS imaging. For achieving high-spatial resolution, the laser beam size was reduced by utilizing an optical fiber with small core diameter (25 μm) in a vacuum matrix-assisted laser desorption ionization-linear ion trap (vMALDI-LTQ) mass spectrometer. Matrix application was greatly improved using oscillating capillary nebulizer. As a result, single cell level spatial resolution of ~ 12 μm was achieved. MS imaging at this high spatial resolution was directly applied to a whole Arabidopsis flower and the substructures of an anther and single pollen grains at the stigma and anther were successfully visualized. MS imaging of high spatial resolution was also demonstrated to the secondary roots of Arabidopsis thaliana and a high degree of localization of detected metabolites was successfully unveiled. This was the first MS imaging on the root for molecular species. MS imaging with high mass resolution was also achieved by utilizing the LTQ-Orbitrap mass spectrometer for the direct identification of the surface metabolites on the Arabidopsis stem and root and differentiation of isobaric ions having the same nominal mass with no need of tandem mass spectrometry (MS/MS). MS imaging at high-spatial and high-mass resolution was also applied to cer1 mutant of the model system Arabidopsis thaliana to demonstrate its usefulness in biological studies and reveal associated metabolite changes in terms of spatial distribution and/or abundances compared to those of wild-type. The spatial

  8. Two-Dimensional Simulation of Mass Transfer in Unitized Regenerative Fuel Cells under Operation Mode Switching

    Directory of Open Access Journals (Sweden)

    Lulu Wang

    2016-01-01

    Full Text Available A two-dimensional, single-phase, isothermal, multicomponent, transient model is built to investigate the transport phenomena in unitized regenerative fuel cells (URFCs under the condition of switching from the fuel cell (FC mode to the water electrolysis (WE mode. The model is coupled with an electrochemical reaction. The proton exchange membrane (PEM is selected as the solid electrolyte of the URFC. The work is motivated by the need to elucidate the complex mass transfer and electrochemical process under operation mode switching in order to improve the performance of PEM URFC. A set of governing equations, including conservation of mass, momentum, species, and charge, are considered. These equations are solved by the finite element method. The simulation results indicate the distributions of hydrogen, oxygen, water mass fraction, and electrolyte potential response to the transient phenomena via saltation under operation mode switching. The hydrogen mass fraction gradients are smaller than the oxygen mass fraction gradients. The average mass fractions of the reactants (oxygen and hydrogen and product (water exhibit evident differences between each layer in the steady state of the FC mode. By contrast, the average mass fractions of the reactant (water and products (oxygen and hydrogen exhibit only slight differences between each layer in the steady state of the WE mode. Under either the FC mode or the WE mode, the duration of the transient state is only approximately 0.2 s.

  9. FluTyper-an algorithm for automated typing and subtyping of the influenza virus from high resolution mass spectral data

    Directory of Open Access Journals (Sweden)

    Schwahn Alexander B

    2010-05-01

    Full Text Available Abstract Background High resolution mass spectrometry has been employed to rapidly and accurately type and subtype influenza viruses. The detection of signature peptides with unique theoretical masses enables the unequivocal assignment of the type and subtype of a given strain. This analysis has, to date, required the manual inspection of mass spectra of whole virus and antigen digests. Results A computer algorithm, FluTyper, has been designed and implemented to achieve the automated analysis of MALDI mass spectra recorded for proteolytic digests of the whole influenza virus and antigens. FluTyper incorporates the use of established signature peptides and newly developed naïve Bayes classifiers for four common influenza antigens, hemagglutinin, neuraminidase, nucleoprotein, and matrix protein 1, to type and subtype the influenza virus based on their detection within proteolytic peptide mass maps. Theoretical and experimental testing of the classifiers demonstrates their applicability at protein coverage rates normally achievable in mass mapping experiments. The application of FluTyper to whole virus and antigen digests of a range of different strains of the influenza virus is demonstrated. Conclusions FluTyper algorithm facilitates the rapid and automated typing and subtyping of the influenza virus from mass spectral data. The newly developed naïve Bayes classifiers increase the confidence of influenza virus subtyping, especially where signature peptides are not detected. FluTyper is expected to popularize the use of mass spectrometry to characterize influenza viruses.

  10. Comprehensive characterisation of flame retardants in textile furnishings by ambient high resolution mass spectrometry, gas chromatography-mass spectrometry and environmental forensic microscopy.

    Science.gov (United States)

    Ionas, Alin C; Ballesteros Gómez, Ana; Uchida, Natsuyo; Suzuki, Go; Kajiwara, Natsuko; Takata, Kyoko; Takigami, Hidetaka; Leonards, Pim E G; Covaci, Adrian

    2015-10-01

    The presence and levels of flame retardants (FRs), such as polybrominated diphenyl ethers (PBDEs) and organophosphate flame retardants (PFRs), was determined in textile home furnishings, such as carpets and curtains from stores in Belgium. A comprehensive characterisation of FRs in textile was done by ambient high resolution mass spectrometry (qualitative screening), gas chromatography-mass spectrometry (GC-MS) (quantitation), and environmental forensic microscopy (surface distribution). Ambient ionisation coupled to a time-of-flight (TOF) high resolution mass spectrometer (direct probe-TOF-MS) was investigated for the rapid screening of FRs. Direct probe-TOF-MS proved to be useful for a first screening step of textiles to detect FRs below the levels required to impart flame retardancy and to reduce, in this way, the number of samples for further quantitative analysis. Samples were analysed by GC-MS to confirm the results obtained by ambient mass spectrometry and to obtain quantitative information. The levels of PBDEs and PFRs were typically too low to impart flame retardancy. Only high levels of BDE-209 (11-18% by weight) were discovered and investigated in localised hotspots by employing forensic microscopy techniques. Most of the samples were made of polymeric materials known to be inherently flame retarded to some extent, so it is likely that other alternative and halogen-free FR treatments/solutions are preferred for the textiles on the Belgian market. Copyright © 2015 Elsevier Inc. All rights reserved.

  11. High-angular resolution observations towards OMC-2 FIR 4: Dissecting an intermediate-mass protocluster

    NARCIS (Netherlands)

    A. López-Sepulcre; V. Taquet; A. Sánchez-Monge; C. Ceccarelli; C. Dominik; M. Kama; E. Caux; F. Fontani; A. Fuente; P.T.P. Ho; R. Neri; Y. Shimajiri

    2013-01-01

    Context. Intermediate-mass stars are an important ingredient of our Galaxy and a key to understanding how high- and low-mass stars form in clusters. One of the closest known young intermediate-mass protoclusters is OMC-2 FIR 4, which is located at a distance of 420 pc in Orion. This region is one of

  12. Ambient Aerosol in Southeast Asia: High Resolution Aerosol Mass Spectrometer Measurements Over Oil Palm (Elaeis guineensis)

    Science.gov (United States)

    Phillips, G.; Dimarco, C.; Misztal, P.; Nemitz, E.; Farmer, D.; Kimmel, J.; Jimenez, J.

    2008-12-01

    The emission of organic compounds in the troposphere is important factor in the formation of secondary organic aerosol (SOA). A very large proportion of organic material emitted globally is estimated to arise from biogenic sources, with almost half coming from tropical and sub-tropical forests. Preliminary analyses of leave cuvette emission studies suggest that oil palm (Elaeis guineensis) is a significantly larger source of isoprene than tropical forest. Much larger sources of isoprene over oil palm allied with a larger anthropogenic component of local emissions contrast greatly with the remote tropical forest environment and therefore the character of SOA formed may differ significantly. These issues, allied with the high price of palm oil on international markets leading to increased use of land for oil palm production, could give rise to rapidly changing chemical and aerosol regimes in the tropics. It is therefore important to understand the current emissions and composition of organic aerosol over all important land-uses in the tropical environment. This in turn will lead to a greater understanding of the present, and to an improvement in predictive capacity for the future system. To help address these issues, a high resolution time of flight aerosol mass spectrometer (HR-ToF-AMS) was deployed in the Sabahmas (PPB OIL) oil palm plantation near Lahad Datu, in Eastern Sabah, as part of the field component of the Aerosol Coupling in the Earth System (ACES) project, part of the UK NERC APPRAISE program. This project was allied closely with measurements made of similar chemical species and aerosol components at a forest site in the Danum Valley as part of the UK Oxidant and Particle Photochemical Processes above a Southeast Asian tropical rainforest (OP3) project. Measurements of submicron non- refractory aerosol composition are presented along with some preliminary analysis of chemically resolved aerosol fluxes made with a new eddy covariance system, based on the

  13. Sequential extraction protocol for organic matter from soils and sediments using high resolution mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Tfaily, Malak M.; Chu, Rosalie K.; Toyoda, Jason; Toli?, Nikola; Robinson, Errol W.; Pa?a-Toli?, Ljiljana; Hess, Nancy J.

    2017-03-31

    A vast number of organic compounds are present in soil organic matter (SOM) and play an important role in the terrestrial carbon cycle, facilitate interactions between organisms, and represent a sink for atmospheric CO2. The diversity of different SOM compounds and their molecular characteristics is a function of the organic source material and biogeochemical history. By understanding how SOM composition changes with sources and the processes by which it is biogeochemically altered in different terrestrial ecosystems, it may be possible to predict nutrient and carbon cycling, response to system perturbations, and impact of climate change will have on SOM composition. In this study, a sequential chemical extraction procedure was developed to reveal the diversity of organic matter (OM) in different ecosystems and was compared to the previously published protocol using parallel solvent extraction (PSE). We compared six extraction methods using three sample types, peat soil, spruce forest soil and river sediment, so as to select the best method for extracting a representative fraction of organic matter from soils and sediments from a wide range of ecosystems. We estimated the extraction yield of dissolved organic carbon (DOC) by total organic carbon analysis, and measured the composition of extracted OM using high resolution mass spectrometry. This study showed that OM composition depends primarily on soil and sediment characteristics. Two sequential extraction protocols, progressing from polar to non-polar solvents, were found to provide the highest number and diversity of organic compounds extracted from the soil and sediments. Water (H2O) is the first solvent used for both protocols followed by either co-extraction with methanol-chloroform (MeOH-CHCl3) mixture, or acetonitrile (ACN) and CHCl3 sequentially. The sequential extraction protocol developed in this study offers improved sensitivity, and requires less sample compared to the PSE workflow where a new sample

  14. Non-target screening with high-resolution mass spectrometry : critical review using a collaborative trial on water analysis

    OpenAIRE

    Emma L. Schymanski; Singer, Heinz P.; Slobodnik, Jaroslav; Onghena, Matthias; et al

    2015-01-01

    Abstract: In this article, a dataset from a collaborative non-target screening trial organised by the NORMAN Association is used to review the state-of-the-art and discuss future perspectives of non-target screening using high-resolution mass spectrometry in water analysis. A total of 18 institutes from 12 European countries analysed an extract of the same water sample collected from the River Danube with either one or both of liquid and gas chromatography coupled with mass spectrometry detec...

  15. High-resolution methods for preserving the sum of mass fractions: improved χ-scheme and an alternative

    Energy Technology Data Exchange (ETDEWEB)

    Syamial, Madhava [National Energy Technology Lab. (NETL), Morgantown, WV (United States); Benyahia, Sofiane [National Energy Technology Lab. (NETL), Morgantown, WV (United States)

    2013-11-20

    When high resolution convection schemes are used for discretizing chemical species mass balance equations, the mass fractions are not guaranteed to add to one. We show that a proposed remedy called χ-scheme (Darwish and Moukalled, Comput.Methods Appl.Mech. Engrg. 192 (2003): 1711) will degrade to a diffusive first-order scheme when a chemical species vanishes from the mixture, for example, because of chemical reactions. We propose an improvement to the χ-scheme to overcome this problem. Furthermore, a computationally efficient alternative scheme is proposed and evaluated with several examples, to quantify the improvements in the accuracy and the computational time.

  16. Grayscale Conterminous United States Shaded Relief ? 200-Meter Resolution - Direct Download

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — The grayscale conterminous United States shaded relief data were derived from National Elevation Dataset (NED) data, and show the terrain of the conterminous United...

  17. Color Conterminous United States Shaded Relief ? 200-Meter Resolution, Albers projection - Direct Download

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — The color conterminous United States shaded relief data were derived from National Elevation Dataset (NED) data, and show the terrain of the conterminous United...

  18. Grayscale Conterminous United States Shaded Relief ? 200-Meter Resolution, Albers projection - Direct Download

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — The grayscale conterminous United States shaded relief data were derived from National Elevation Dataset (NED) data, and show the terrain of the conterminous United...

  19. Color Conterminous United States Shaded Relief ? 200-Meter Resolution - Direct Download

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — The color conterminous United States shaded relief data were derived from National Elevation Dataset (NED) data, and show the terrain of the conterminous United...

  20. Measurement of pyrethroid, organophosphorus, and carbamate insecticides in human plasma using isotope dilution gas chromatography-high resolution mass spectrometry.

    Science.gov (United States)

    Pérez, José J; Williams, Megan K; Weerasekera, Gayanga; Smith, Kimberly; Whyatt, Robin M; Needham, Larry L; Barr, Dana Boyd

    2010-10-01

    We have developed a gas chromatography-high resolution mass spectrometry method for measuring pyrethroid, organophosphorus, carbamate and fipronil pesticides and the synergist piperonyl butoxide in human plasma. Plasma samples were extracted using solid phase extraction and were then concentrated for injection and analysis using isotope dilution gas chromatography-high resolution mass spectrometry. The limits of detection ranged from 10 to 158 pg/mL with relative recoveries at concentrations near the LODs (e.g., 25 or 250 pg/mL) ranging from 87% to 156% (9 of the 16 compounds were within ±15% of 100%). The extraction recoveries ranged from 20% to 98% and the overall method relative standard deviations were typically less than 20% with some exceptions. Analytical characteristics were determined at 25, 250, and 1000 pg/mL.

  1. 21 Tesla Fourier Transform Ion Cyclotron Resonance Mass Spectrometer: A National Resource for Ultrahigh Resolution Mass Analysis.

    Science.gov (United States)

    Hendrickson, Christopher L; Quinn, John P; Kaiser, Nathan K; Smith, Donald F; Blakney, Greg T; Chen, Tong; Marshall, Alan G; Weisbrod, Chad R; Beu, Steven C

    2015-09-01

    We describe the design and initial performance of the first 21 tesla Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. The 21 tesla magnet is the highest field superconducting magnet ever used for FT-ICR and features high spatial homogeneity, high temporal stability, and negligible liquid helium consumption. The instrument includes a commercial dual linear quadrupole trap front end that features high sensitivity, precise control of trapped ion number, and collisional and electron transfer dissociation. A third linear quadrupole trap offers high ion capacity and ejection efficiency, and rf quadrupole ion injection optics deliver ions to a novel dynamically harmonized ICR cell. Mass resolving power of 150,000 (m/Δm(50%)) is achieved for bovine serum albumin (66 kDa) for a 0.38 s detection period, and greater than 2,000,000 resolving power is achieved for a 12 s detection period. Externally calibrated broadband mass measurement accuracy is typically less than 150 ppb rms, with resolving power greater than 300,000 at m/z 400 for a 0.76 s detection period. Combined analysis of electron transfer and collisional dissociation spectra results in 68% sequence coverage for carbonic anhydrase. The instrument is part of the NSF High-Field FT-ICR User Facility and is available free of charge to qualified users.

  2. Decreases in elemental carbon and fine particle mass in the United States

    Directory of Open Access Journals (Sweden)

    D. M. Murphy

    2011-01-01

    Full Text Available Observations at national parks and other remote sites show that average elemental carbon and fine particle mass concentrations in the United States both decreased by over 25% between 1990 and 2004. Percentage decreases in elemental carbon were much larger in winter than in summer. These data suggest that emissions controls have been effective in reducing particulate concentrations not only in polluted areas but also across the United States. Despite the reduction in elemental carbon, the simultaneous decrease in non-absorbing particles implies that the overall radiative forcing from these changes was toward warming. The use of a 2005 instead of 1990 as a baseline for climate-relevant emissions from the United States would imply a significantly lower baseline for aerosol emissions. The use of older data will overestimate the possibility for future reductions in warming due to black carbon controls.

  3. Decreases in elemental carbon and fine particle mass in the United States

    Directory of Open Access Journals (Sweden)

    D. M. Murphy

    2011-05-01

    Full Text Available Observations at national parks and other remote sites show that average elemental carbon and fine particle mass concentrations in the United States both decreased by over 25 % between 1990 and 2004. Percentage decreases in elemental carbon were much larger in winter than in summer. These data suggest that emissions controls have been effective in reducing particulate concentrations not only in polluted areas but also across the United States. Despite the reduction in elemental carbon, the simultaneous decrease in non-absorbing particles implies that the overall radiative forcing from these changes was toward warming. The use of a 2005 instead of 1990 as a baseline for climate-relevant emissions from the United States would imply a significantly lower baseline for aerosol emissions. The use of older data will overestimate the possibility for future reductions in warming due to black carbon controls.

  4. NOAA's Medium Resolution Digital Vector Shoreline (1998) for the Contiguous United States

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — NOAA's Medium Resolution Digital Vector Shoreline is a high-quality, Geographic Information System-ready, general-use digital vector data set created by the...

  5. Desorption electrospray ionization-high resolution mass spectrometry for the screening of veterinary drugs in cross-contaminated feedstuffs.

    Science.gov (United States)

    Seró, Raquel; Núñez, Oscar; Bosch, Jaume; Grases, José M; Rodríguez, Pilar; Moyano, Encarnacion; Galceran, Martia Teresa

    2015-09-01

    In this study, a desorption electrospray ionization-high resolution mass spectrometry (DESI-HRMS) screening method was developed for fast identification of veterinary drugs in cross-contaminated feedstuffs. The reliable detection was performed working at high resolution (70,000 full width half maximum, FWHM) using an orbitrap mass analyzer. Among the optimized DESI parameters, the solvent (acetonitrile/water, 80:20, v/v) and the sample substrate (poly-tetrafluoroethylene, PTFE) were critical to obtain the best sensitivity. To analyze the solid feed samples, different approaches were tested and a simple solid-liquid extraction and the direct analysis of an aliquot (2 μL) of the extract after letting it dry on the PTFE printed spot provided the best results. The identification of the veterinary drugs (target and non-target) in the cross-contaminated feedstuffs based on the accurate mass measurement and the isotopic pattern fit was performed automatically using a custom-made database. The positive cross-contaminated feed samples were quantified by ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). The results obtained demonstrate that DESI-HRMS can be proposed as a fast and suitable screening method to identify positive cross-contaminated feedstuffs reducing the number of samples to be subsequently quantified by UHPLC-MS/MS, thus improving the productivity in quality control laboratories.

  6. High mass and spatial resolution mass spectrometry imaging of Nicolas Poussin painting cross section by cluster TOF-SIMS.

    Science.gov (United States)

    Noun, M; Van Elslande, E; Touboul, D; Glanville, H; Bucklow, S; Walter, P; Brunelle, A

    2016-12-01

    The painting Rebecca and Eliezer at the Well, which hangs in the Fitzwilliam Museum, Cambridge, UK, is possibly one of the last figure painting executed by Nicolas Poussin at the very end of his life and is usually dated to the early 1660s. In this perspective special feature, Philippe Walter, Alain Brunelle and colleagues give new insights on the artist's working methods by a careful stateof-the-art imaging ToF-SIMS study of one sample taken on the edge of the painting. This approach allowed for the identification of the pigments used in the painting, their nature and components and those of the ground and preparatory layers, with the identification of the binder(s) and possible other additions of organic materials such as glue. This study paves the way to a wider use of ToF-SIMS for the analysis of ancient cultural heritage artefacts. Dr. Walter is the Director of the Molecular and Structural Archeology Laboratory (Université Pierre et Marie Curie, Paris, France). Dr. Brunelle is Head of the Mass Spectrometry Laboratory at the Institut de Chimie des Substances Naturelles (CNRS, Gif-sur-Yvette, France). Their long standing collaboration has led to several seminal publications on the analysis of ancient artefacts by mass spectrometry.

  7. Transformation products of emerging contaminants in the environment and high-resolution mass spectrometry: a new horizon.

    Science.gov (United States)

    Picó, Yolanda; Barceló, Damià

    2015-08-01

    It is crucial to study the presence of transformation products (TPs) of emerging contaminants that can be potentially found in the environment after biological or chemical degradation. This review focuses on the potential and shortcomings of high-resolution mass spectrometry (HRMS) to identify these TPs, with emphasis on recent developments in mass analyzers, data evaluation, and compound identification workflows and applications. Advances in HRMS technologies, including direct introduction or in-line chromatographic separation modes, ionization techniques, mass analyzers, and detection methods, have led to powerful tools to assess the molecular changes and the opening of new horizons to identify unknown molecules. Advances in HRMS pertaining to the generation of analytical data for the main methods to identify TPs, including nontargeted and targeted approaches as they are applied to elucidate the structure of TPs, are also discussed.

  8. Metabolite Identification Using Automated Comparison of High-Resolution Multistage Mass Spectral Trees

    NARCIS (Netherlands)

    Rojas-Cherto, M.; Peironcely, J.E.; Kasper, P.T.; Hooft, van der J.J.J.; Vos, de R.C.H.; Vreeken, R.; Hankemeier, T.; Reijmers, T.

    2012-01-01

    Multistage mass spectrometry (MSn) generating so-called spectral trees is a powerful tool in the annotation and structural elucidation of metabolites and is increasingly used in the area of accurate mass LC/MS-based metabolomics to identify unknown, but biologically relevant, compounds. As a consequ

  9. Rapid screening of drugs of abuse in human urine by high-performance liquid chromatography coupled with high resolution and high mass accuracy hybrid linear ion trap-Orbitrap mass spectrometry.

    Science.gov (United States)

    Li, Xiaowen; Shen, Baohua; Jiang, Zheng; Huang, Yi; Zhuo, Xianyi

    2013-08-09

    A novel analytical toxicology method has been developed for the analysis of drugs of abuse in human urine by using a high resolution and high mass accuracy hybrid linear ion trap-Orbitrap mass spectrometer (LTQ-Orbitrap-MS). This method allows for the detection of different drugs of abuse, including amphetamines, cocaine, opiate alkaloids, cannabinoids, hallucinogens and their metabolites. After solid-phase extraction with Oasis HLB cartridges, spiked urine samples were analysed by HPLC/LTQ-Orbitrap-MS using an electrospray interface in positive ionisation mode, with resolving power of 30,000 full width at half maximum (FWHM). Gradient elution off of a Hypersil Gold PFP column (50mm×2.1mm) allowed to resolve 65 target compounds and 3 internal standards in a total chromatographic run time of 20min. Validation of this method consisted of confirmation of identity, selectivity, linearity, limit of detection (LOD), lowest limits of quantification (LLOQ), accuracy, precision, extraction recovery and matrix effect. The regression coefficients (r(2)) for the calibration curves (LLOQ - 100ng/mL) in the study were ≥0.99. The LODs for 65 validated compounds were better than 5ng/ml except for 4 compounds. The relative standard deviation (RSD), which was used to estimate repeatability at three concentrations, was always less than 15%. The recovery of extraction and matrix effects were above 50 and 70%, respectively. Mass accuracy was always better than 2ppm, corresponding to a maximum mass error of 0.8 millimass units (mmu). The accurate masses of characteristic fragments were obtained by collisional experiments for a more reliable identification of the analytes. Automated data analysis and reporting were performed using ToxID software with an exact mass database. This procedure was then successfully applied to analyse drugs of abuse in a real urine sample from subject who was assumed to be drug addict.

  10. Structural Characterization of a Thrombin-Aptamer Complex by High Resolution Native Top-Down Mass Spectrometry

    Science.gov (United States)

    Zhang, Jiang; Loo, Rachel R. Ogorzalek; Loo, Joseph A.

    2017-09-01

    Native mass spectrometry (MS) with electrospray ionization (ESI) has evolved as an invaluable tool for the characterization of intact native proteins and non-covalently bound protein complexes. Here we report the structural characterization by high resolution native top-down MS of human thrombin and its complex with the Bock thrombin binding aptamer (TBA), a 15-nucleotide DNA with high specificity and affinity for thrombin. Accurate mass measurements revealed that the predominant form of native human α-thrombin contains a glycosylation mass of 2205 Da, corresponding to a sialylated symmetric biantennary oligosaccharide structure without fucosylation. Native MS showed that thrombin and TBA predominantly form a 1:1 complex under near physiological conditions (pH 6.8, 200 mM NH4OAc), but the binding stoichiometry is influenced by the solution ionic strength. In 20 mM ammonium acetate solution, up to two TBAs were bound to thrombin, whereas increasing the solution ionic strength destabilized the thrombin-TBA complex and 1 M NH4OAc nearly completely dissociated the complex. This observation is consistent with the mediation of thrombin-aptamer binding through electrostatic interactions and it is further consistent with the human thrombin structure that contains two anion binding sites on the surface. Electron capture dissociation (ECD) top-down MS of the thrombin-TBA complex performed with a high resolution 15 Tesla Fourier transform ion cyclotron resonance (FTICR) mass spectrometer showed the primary binding site to be at exosite I located near the N-terminal sequence of the heavy chain, consistent with crystallographic data. High resolution native top-down MS is complementary to traditional structural biology methods for structurally characterizing native proteins and protein-DNA complexes. [Figure not available: see fulltext.

  11. DETECTING LOW-LEVEL SYNTHESIS IMPURITIES IN MODIFIED PHOSPHOROTHIOATE OLIGONUCLEOTIDES USING LIQUID CHROMATOGRAPHY - HIGH RESOLUTION MASS SPECTROMETRY.

    Science.gov (United States)

    Nikcevic, Irena; Wyrzykiewicz, Tadeusz K; Limbach, Patrick A

    2011-07-01

    An LC-MS method based on the use of high resolution Fourier transform ion cyclotron resonance mass spectrometry (FTIRCMS) for profiling oligonucleotides synthesis impurities is described.Oligonucleotide phosphorothioatediesters (phosphorothioate oligonucleotides), in which one of the non-bridging oxygen atoms at each phosphorus center is replaced by a sulfur atom, are now one of the most popular oligonucleotide modifications due to their ease of chemical synthesis and advantageous pharmacokinetic properties. Despite significant progress in the solid-phase oligomerization chemistry used in the manufacturing of these oligonucleotides, multiple classes of low-level impurities always accompany synthetic oligonucleotides. Liquid chromatography-mass spectrometry has emerged as a powerful technique for the identification of these synthesis impurities. However, impurity profiling, where the entire complement of low-level synthetic impurities is identified in a single analysis, is more challenging. Here we present an LC-MS method based the use of high resolution-mass spectrometry, specifically Fourier transform ion cyclotron resonance mass spectrometry (FTIRCMS or FTMS). The optimal LC-FTMS conditions, including the stationary phase and mobile phases for the separation and identification of phosphorothioate oligonucleotides, were found. The characteristics of FTMS enable charge state determination from single m/z values of low-level impurities. Charge state information then enables more accurate modeling of the detected isotopic distribution for identification of the chemical composition of the detected impurity. Using this approach, a number of phosphorothioate impurities can be detected by LC-FTMS including failure sequences carrying 3'-terminal phosphate monoester and 3'-terminal phosphorothioate monoester, incomplete backbone sulfurization and desulfurization products, high molecular weight impurities, and chloral, isobutyryl, and N(3) (2-cyanoethyl) adducts of the full

  12. Accurate correction of magnetic field instabilities for high-resolution isochronous mass measurements in storage rings

    CERN Document Server

    Shuai, P; Zhang, Y H; Litvinov, Yu A; Wang, M; Tu, X L; Blaum, K; Zhou, X H; Yuan, Y J; Audi, G; Yan, X L; Chen, X C; Xu, X; Zhang, W; Sun, B H; Yamaguchi, T; Chen, R J; Fu, C Y; Ge, Z; Huang, W J; Liu, D W; Xing, Y M; Zeng, Q

    2014-01-01

    Isochronous mass spectrometry (IMS) in storage rings is a successful technique for accurate mass measurements of short-lived nuclides with relative precision of about $10^{-5}-10^{-7}$. Instabilities of the magnetic fields in storage rings are one of the major contributions limiting the achievable mass resolving power, which is directly related to the precision of the obtained mass values. A new data analysis method is proposed allowing one to minimise the effect of such instabilities. The masses of the previously measured at the CSRe $^{41}$Ti, $^{43}$V, $^{47}$Mn, $^{49}$Fe, $^{53}$Ni and $^{55}$Cu nuclides were re-determined with this method. An improvement of the mass precision by a factor of $\\sim 1.7$ has been achieved for $^{41}$Ti and $^{43}$V. The method can be applied to any isochronous mass experiment irrespective of the accelerator facility. Furthermore, the method can be used as an on-line tool for checking the isochronous conditions of the storage ring.

  13. [Determination of mono- to tri-chlorinated dibenzo-p-dioxins and dibenzofurans in stack gas using isotope dilution high resolution gas chromatography-high resolution mass spectrometry].

    Science.gov (United States)

    Tang, Chen; Liu, Qipeng; Tian, Zhenyu; Xie, Huiting; Wang, Mengjing; Liu, Wenbin

    2014-09-01

    A method for the determination of mono- to tri-chlorinated dibenzo-p-dioxins and dibenzofurans (mono- to tri-CDD/Fs) in stack gas using isotope dilution high resolution gas chromatography-high resolution mass spectrometry (HRGC-HRMS) was developed. The sam- ples were extracted by Soxhlet extraction, and then the extracts were concentrated and purified using a multilayer silica gel column and a basic alumina column. The analytes were separated by HRGC on a DB-5MS column (30 m x 0.25 mm x 0.25 μm) and determined by HRMS. The identi- fication of mono- to tri-CDD/Fs was based on the retention times of 13C-labelled standard and the abundance ratios of the two exacted mass-to-charge ratios. The quantitative analysis was performed using the ratios of the integrated areas of the 13C-labelled standards. This method had the recoveries ranging from 66.6% to 112.5% and the relative standard deviations (RSD) ranging from 19.9% to 40.5% (n = 5). The limits of detection (LODs) of this method for the mono- to tri-CDD/Fs were ranging from 0.027 to 0.485 μg/L. Three stack gas samples from waste incinerators were measured using this method, with the recoveries ranging from 85.7% to 137.0% and the concentrations ranging from 11.4 to 9,183 pg/Nm3. The results indicated that the method can be applied to the precise determination of mono- to tri-CDD/Fs at trace level in stack gas.

  14. High mass resolution, high angular acceptance time-of-flight mass spectroscopy for planetary missions under the Planetary Instrument Definition and Development Program (PIDDP)

    Science.gov (United States)

    Young, David T.

    1991-01-01

    This final report covers three years and several phases of work in which instrumentation for the Planetary Instrument Definition and Development Program (PIDDP) were successfully developed. There were two main thrusts to this research: (1) to develop and test methods for electrostatically scanning detector field-of-views, and (2) to improve the mass resolution of plasma mass spectrometers to M/delta M approximately 25, their field-of-view (FOV) to 360 degrees, and their E-range to cover approximately 1 eV to 50 keV. Prototypes of two different approaches to electrostatic scanning were built and tested. The Isochronous time-of-flight (TOF) and the linear electric field 3D TOF devices were examined.

  15. Non-targeted analysis of electronics waste by comprehensive two-dimensional gas chromatography combined with high-resolution mass spectrometry: Using accurate mass information and mass defect analysis to explore the data.

    Science.gov (United States)

    Ubukata, Masaaki; Jobst, Karl J; Reiner, Eric J; Reichenbach, Stephen E; Tao, Qingping; Hang, Jiliang; Wu, Zhanpin; Dane, A John; Cody, Robert B

    2015-05-22

    Comprehensive two-dimensional gas chromatography (GC×GC) and high-resolution mass spectrometry (HRMS) offer the best possible separation of their respective techniques. Recent commercialization of combined GC×GC-HRMS systems offers new possibilities for the analysis of complex mixtures. However, such experiments yield enormous data sets that require new informatics tools to facilitate the interpretation of the rich information content. This study reports on the analysis of dust obtained from an electronics recycling facility by using GC×GC in combination with a new high-resolution time-of-flight (TOF) mass spectrometer. New software tools for (non-traditional) Kendrick mass defect analysis were developed in this research and greatly aided in the identification of compounds containing chlorine and bromine, elements that feature in most persistent organic pollutants (POPs). In essence, the mass defect plot serves as a visual aid from which halogenated compounds are recognizable on the basis of their mass defect and isotope patterns. Mass chromatograms were generated based on specific ions identified in the plots as well as region of the plot predominantly occupied by halogenated contaminants. Tentative identification was aided by database searches, complementary electron-capture negative ionization experiments and elemental composition determinations from the exact mass data. These included known and emerging flame retardants, such as polybrominated diphenyl ethers (PBDEs), hexabromobenzene, tetrabromo bisphenol A and tris (1-chloro-2-propyl) phosphate (TCPP), as well as other legacy contaminants such as polychlorinated biphenyls (PCBs) and polychlorinated terphenyls (PCTs).

  16. [The rapid analysis of polychlorinated quaterphenyls in blood using different diameter capillary column with the high-resolution gas chromatograph high-resolution mass spectrometer].

    Science.gov (United States)

    Yasutake, Daisuke; Ashizuka, Yuki; Hori, Tsuguhide; Kurokawa, Youichi; Kajiwara, Jumboku; Hirata, Teruaki; Ishiguro, Yasuhisa; Iida, Takao; Uchi, Hiroshi; Furue, Masutaka

    2011-04-01

    The polychlorinated quaterphenyl (PCQ) concentrations in blood are important discriminative parameters in yusho patient. In this study, a rapid analytical method for PCQ using different diameter capillary column (rapid-Rtx65TG) with high-resolution gas chromatograph high-resolution mass spectrometer (HRGC/HRMS) instead of the gas chromatograph electron capture detector (ECD/GC) was developed. Using different diameter capillary columns, the analysis time of the HRGC/HRMS was drastically shortened, and the detection sensitivity was improved. In the rapid-Rtx65TG column, a small-bore capillary column (length 1m, I.D. 0.1mm) was connected with the inlet side of the GC, and behind that column, a large-bore capillary column (length 15mm, I.D. 0.53mm) for octadecachloroquaterphenyl (ODCQ) analysis was connected. In the HRGC/HRMS measurement of ODCQ by the rapid-Rtx65TG column, the minimum limit of detection for the apparatus was 0.4 pg, and the minimum limit of determination for the blood was 0.008 ppb. On ECD/GC in the conventional method and HRGC/HRMS in this study, the PCQ concentration in blood including yusho patients and yusho suspected persons was almost equivalent.

  17. Very high resolution surface mass balance over Greenland modeled by the regional climate model MAR with a downscaling technique

    Science.gov (United States)

    Kittel, Christoph; Lang, Charlotte; Agosta, Cécile; Prignon, Maxime; Fettweis, Xavier; Erpicum, Michel

    2016-04-01

    This study presents surface mass balance (SMB) results at 5 km resolution with the regional climate MAR model over the Greenland ice sheet. Here, we use the last MAR version (v3.6) where the land-ice module (SISVAT) using a high resolution grid (5km) for surface variables is fully coupled while the MAR atmospheric module running at a lower resolution of 10km. This online downscaling technique enables to correct near-surface temperature and humidity from MAR by a gradient based on elevation before forcing SISVAT. The 10 km precipitation is not corrected. Corrections are stronger over the ablation zone where topography presents more variations. The model has been force by ERA-Interim between 1979 and 2014. We will show the advantages of using an online SMB downscaling technique in respect to an offline downscaling extrapolation based on local SMB vertical gradients. Results at 5 km show a better agreement with the PROMICE surface mass balance data base than the extrapolated 10 km MAR SMB results.

  18. Correlation of precursor and product ions in single-stage high resolution mass spectrometry. A tool for detecting diagnostic ions and improving the precursor elemental composition elucidation

    Energy Technology Data Exchange (ETDEWEB)

    Borràs, S. [Departament de Química Analítica, Universitat de Barcelona, Martí i Franquès 1-11, 08028 Barcelona (Spain); Kaufmann, A., E-mail: anton.kaufmann@klzh.ch [Official Food Control Authority, Fehrenstrasse 15, 8032 Zürich (Switzerland); Companyó, R. [Departament de Química Analítica, Universitat de Barcelona, Martí i Franquès 1-11, 08028 Barcelona (Spain)

    2013-04-15

    Highlights: ► We are describing a technique to spot ions which are derived from each other. ► Single stage high resolution data is used. ► This “in silicon” technique is compared to conventional precursor scan. ► Some applications for this technique are presented. -- Abstract: Monitoring of common diagnostic fragments is essential for recognizing molecules which are members of a particular compound class. Up to now, unit resolving tandem quadrupole mass spectrometers, operating in the precursor ion scan mode, have been typically used to perform such analysis. By means of high-resolution mass spectrometry (HRMS) a much more sensitive and selective detection can be achieved. However, using a single-stage HRMS instrument, there is no unequivocal link to the corresponding precursor ion, since such instrumentation does not permit a previous precursor selection. Thus, to address this limitation, an in silico approach to locate precursor ions, based on diagnostic fragments, was developed. Implemented as an Excel macro, the algorithm rapidly assembles and surveys exact mass data to provide a list of feasible precursor candidates according to the correlation of the chromatographic peak shape profile and other additional filtering criteria (e.g. neutral losses and isotopes). The macro was tested with two families of veterinary drugs, sulfonamides and penicillins, which are known to yield diagnostic product ions when fragmented. Data sets obtained from different food matrices (fish and liver), both at high and low concentration of the target compounds, were investigated in order to evaluate the capabilities and limitations of the reported approach. Finally, other possible applications of this technique, such as the elucidation of elemental compositions based on product ions and corresponding neutral losses, were also presented and discussed.

  19. Maximal neutron star mass and the resolution of hyperon puzzle in modified gravity

    CERN Document Server

    Astashenok, Artyom V; Odintsov, Sergei D

    2014-01-01

    The so-called hyperon puzzle in the theory of neutron stars is considered in the framework of modified $f(R)$ gravity. We show that for simple hyperon equations of state, it is possible to obtain the maximal neutron star mass which satisfies the recent observational data for PSR J1614-2230, in higher-derivative models with power-law terms as $f(R) = R+\\alpha R^2+ \\beta R^3$. The soft hyperon equation of state under consideration is usually treated as non-realistic in the standard General Relativity. The numerical analysis of Mass-Radius relation for massive neutron stars with hyperon equation of state in modified gravity turns out to be consistent with observations. Thus, we show that the same modified gravity can solve at once three problems: consistent description of the maximal mass of neutron star, realistic Mass-Radius relation and account for hyperons in equation of state.

  20. Improved Resolution of Hydrocarbon Structures and Constitutional Isomers in Complex Mixtures Using Gas Chromatography-Vacuum Ultraviolet-Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Isaacman, Gabriel [Univ. of California, Berkeley, CA (United States); Wilson, Kevin R. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Chan, Arthur W. H. [Univ. of California, Berkeley, CA (United States); Worton, David R. [Univ. of California, Berkeley, CA (United States). Aerosol Dynamics Inc., Berkeley, CA (United States); Kimmel, Joel R. [Aerodyne Research, Inc., Billerica, MA (United States); Univ. of Colorado, Boulder, CO (United States). Tofwerk AG, Thun (Switzerland); Nah, Theodora [Univ. of California, Berkeley, CA (United States); Hohaus, Thorsten [Aerodyne Research, Inc., Billerica, MA (United States); Gonin, Marc [Tofwerk AG, Thun (Switzerland); Kroll, Jesse H. [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Worsnop, Douglas R. [Aerodyne Research, Inc., Billerica, MA (United States); Goldstein, Allen H. [Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

    2012-01-30

    Understanding the composition of complex hydrocarbon mixtures is important for environmental studies in a variety of fields, but many prevalent compounds cannot be confidently identified using traditional gas chromatography/mass spectrometry (GC/MS) techniques. In this study, we use vacuum-ultraviolet (VUV) ionization to elucidate the structures of a traditionally “unresolved complex mixture” by separating components by GC retention time, tR, and mass-to-charge ratio, m/z, which are used to determine carbon number, NC, and the number of rings and double bonds, NDBE. Constitutional isomers are resolved on the basis of tR, enabling the most complete quantitative analysis to date of structural isomers in an environmentally relevant hydrocarbon mixture. Unknown compounds are classified in this work by carbon number, degree of saturation, presence of rings, and degree of branching, providing structural constraints. The capabilities of this analysis are explored using diesel fuel, in which constitutional isomer distribution patterns are shown to be reproducible between carbon numbers and follow predictable rules. Nearly half of the aliphatic hydrocarbon mass is shown to be branched, suggesting branching is more important in diesel fuel than previously shown. Lastly, the classification of unknown hydrocarbons and the resolution of constitutional isomers significantly improves resolution capabilities for any complex hydrocarbon mixture.

  1. Causes of Forest Fragmentation in the United States ? 1 Kilometer Resolution - Direct Download

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — This map layer is a grid map of the conterminous United States, created from National Land Cover Data (NLCD). The NLCD data was reclassified into four categories:...

  2. USGS Small-scale Dataset - 100-Meter Resolution Elevation of the Conterminous United States 201212 TIFF

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — This map layer contains elevation data for the conterminous United States, in an Albers Equal-Area Conic projection. The elevation data were derived from National...

  3. 100-Meter Resolution Elevation of the Conterminous United States - Direct Download

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — This map layer contains elevation data for the conterminous United States, in an Albers Equal-Area Conic projection. The elevation data were derived from National...

  4. 100-Meter Resolution Natural Earth of the Conterminous United States - Direct Download

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — This map layer contains a natural-earth image of the conterminous United States. The image is land cover in natural colors combined with shaded relief, which...

  5. Causes of Forest Fragmentation in the United States ? 270 Meter Resolution - Direct Download

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — This map layer is a grid map of the conterminous United States, created from National Land Cover Data (NLCD). The NLCD data was reclassified into four categories:...

  6. Causes of Forest Fragmentation in the United States - 540 Meter Resolution - Direct Download

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — This map layer is a grid map of the conterminous United States, created from National Land Cover Data (NLCD). The NLCD data was reclassified into four categories:...

  7. On the conversion of tritium units to mass fractions for hydrologic applications.

    Science.gov (United States)

    Stonestrom, David A; Andraski, Brian J; Cooper, Clay A; Mayers, C Justin; Michel, Robert L

    2013-06-01

    We develop a general equation for converting laboratory-reported tritium levels, expressed either as concentrations (tritium isotope number fractions) or mass-based specific activities, to mass fractions in aqueous systems. Assuming that all tritium is in the form of monotritiated water simplifies the derivation and is shown to be reasonable for most environmental settings encountered in practice. The general equation is nonlinear. For tritium concentrations c less than 4.5 × 10(12) tritium units (TU) - i.e. specific tritium activitiestritium isotopes in the absence of sample-specific data. Variation in the relative abundances of non-tritium isotopes in the terrestrial hydrosphere produces a minimum range for the mantissa of the conversion factor of [2.22287; 2.22300].

  8. Direct Determination of Trace Impurities in High Purity Zinc Oxide by High Resolution Inductively Coupled Plasma Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    XIE Hualin; NIE Xidu; LI Libo; SONG Chuhua

    2006-01-01

    The determination of trace impurities in high purity zinc oxide by high resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) was investigated. To overcome some potentially problematic spectral interference, measurements were acquired in both middle and high resolution modes. The matrix effects due to the presence of excess HCl and zinc were evaluated. The optimum conditions for the determination were tested and discussed. The standard addition method was employed for quantitative analysis. The detection limits ranged from 0.02 μg/g to 6 μg/g depending on the elements.The experimental results for the determination of Na, Mg, Ca, Cr, Mn, Fe, Co, Ni, Cu, Mo, Cd, Sb and Pb in several high purity zinc oxide powders were presented.

  9. Social media as an instrument for organizing mass riots in the United Kingdom in August 2011

    Directory of Open Access Journals (Sweden)

    A N Katkina

    2015-12-01

    Full Text Available Social networks such as Facebook and Twitter have recently become very popular and turned to be an effective instrument for achieving political goals. However, the social networks’ impact is rather ambivalent: on the one hand, social media form specific political actors and support self-organization and civil movements; on the other hand, social media reinforce destructive and aggressive manifestations with the pronounced criminal purposes, e.g. social media ability to disseminate information among large groups is used to organize mass riots. The article analyzes one of the recent and significant events largely provoked by the social networks - mass riots in the United Kingdom in August 2011 that were originally a reaction to the murder of M. Diggan by a police officer who tried to arrest him as a suspect in drug trafficking and possession of weapons. The way events developed into mass riots was the result of discussions in social media and use of social networks to coordinate joint actions of mass riots participants. The article provides a detailed description of the events and authorities’ actions to overcome the crisis and prevent such riots in the future, thus making some conclusions about the nature of social media impact on the politics.

  10. Very high resolution modelling of the Surface Mass Balance of the Greenland Ice Sheet: Present day conditions and future prospects.

    Science.gov (United States)

    Mottram, Ruth; Aðalgeirsdóttir, Guðfinna; Boberg, Fredrik; Hesselbjerg Christensen, Jens; Bøssing Christensen, Ole; Langen, Peter; Rodehacke, Christian; Stendel, Martin; Yang, Shuting

    2014-05-01

    Recent experiments with the Regional Climate Model (RCM) HIRHAM5 have produced new surface mass balance (SMB) estimates at the unprecedented high horizontal resolution of 0.05 degrees (~5.5km). These simulations indicate a present day SMB of 347 ± 98 Gt/year over the whole ice sheet averaged over the period 1989 - 2012 driven by the ERA-Interim reanalysis dataset. We validate accumulation rates over the ice sheet using estimates from shallow firn cores to confirm the importance of resolution to accurate estimates of accumulation. Comparison with PROMICE and GC-Net automatic weather station observations shows the model represents present day climate and climate variability well when driven by the ERA-Interim reanalysis dataset. Comparison with a simulation at 0.25 degrees (~27km) resolution from the same model shows a significantly different calculated SMB over the whole ice sheet, largely due to changes in precipitation distribution over Greenland. The very high resolution requires a more sophisticated treatment of sub-grid scale processes in the snow pack including meltwater retention and refreezing and an enhanced albedo scheme. Our results indicate retention processes account for a significant proportion of the total surface budget based on a new parameterization scheme in the model. SMB projections, driven by the EC-Earth Global Climate Model (GCM) at the boundaries for the RCP 4.5 scenario indicate a declining surface mass balance over the 21st century with some compensation for warmer summer temperatures and enhanced melt in the form of increased precipitation. A cold bias in the driving GCM for present day conditions suggests that this simulation likely underestimates the change in SMB. However, the downscaled precipitation fields compare well with those in the reanalysis driven simulations. A soon-to-be complete simulation uses driving fields from the GCM running the RCP8.5 scenario.

  11. A mass resolved, high resolution neutral particle analyzer for C-2U

    Science.gov (United States)

    Clary, R.; Roquemore, A.; Douglass, J.; Jaramillo, D.; Korepanov, S.; Magee, R.; Medley, S.; Smirnov, A.

    2016-11-01

    C-2U is a high-confinement, advanced beam driven field-reversed configuration plasma experiment which sustains the configuration for >5 ms, in excess of typical MHD and fast particle instability times, as well as fast particle slowing down times. Fast particle dynamics are critical to C-2U performance and several diagnostics have been deployed to characterize the fast particle population, including neutron and proton detectors. To increase our understanding of fast particle behavior and supplement existing diagnostics, an E ∥ B neutral particle analyzer was installed, which simultaneously measures H0 and D0 flux with large dynamic range and high energy resolution. Here we report the commissioning of the E ∥ B analyzer, confirm the instrument has energy resolution Δ E / E ≲ 0 . 1 and a dynamic range E max / E min ˜ 30 , and present measurements of initial testing on C-2U.

  12. Determination of volatile components in cut tobacco with gas chromatography-mass spectrometry and chemometric resolution

    Institute of Scientific and Technical Information of China (English)

    HUANG Lan-fang; WU Ming-jian; SUN Xian-jun; ZHONG Ke-jun; GUO Zi-ming; DAI Yun-hui; HUANG Ke-long; GUO Fang-qiu

    2007-01-01

    Chromatography-mass spectrometry (GC-MS) was used to analyze the volatile components of cut tobacco samples with the help of heuristic evolving latent projections (HELP). After extracting with simultaneous distillation and extraction method, the volatile components in cut tobacco were detected by GC-MS. Then the obtained original two-dimensional data were resolved into pure mass spectra and chromatograms. The qualitative analysis was performed by similarity searches in the national institute of standards and technology(NIST) mass database with the obtained pure mass spectrum of each component and the quantitative results were obtained by calculating the volume of total two-way response. The accuracy of qualitative and quantitative results were greatly improved by using the two-dimensional comprehensive information of chromatograms and mass spectra. 107 of 141 separated constituents in the total ion chromatogram of the volatile components were identified and quantified, accounting for about 88.01% of the total content. The result proves that the developed method is powerful for the analysis of complex cut tobacco samples.

  13. “Lossless” compression of high resolution mass spectra of small molecules

    Science.gov (United States)

    Blanckenburg, Bo; van der Burgt, Yuri E. M.; Deelder, André M.

    2010-01-01

    Fourier transform ion cyclotron resonance (FTICR) provides the highest resolving power of any commercially available mass spectrometer. This advantage is most significant for species of low mass-to-charge ratio (m/z), such as metabolites. Unfortunately, FTICR spectra contain a very large number of data points, most of which are noise. This is most pronounced at the low m/z end of spectra, where data point density is the highest but peak density low. We therefore developed a filter that offers lossless compression of FTICR mass spectra from singly charged metabolites. The filter relies on the high resolving power and mass measurement precision of FTICR and removes only those m/z channels that cannot contain signal from singly charged organic species. The resulting pseudospectra still contain the same signal as the original spectra but less uninformative background. The filter does not affect the outcome of standard downstream chemometric analysis methods, such as principal component analysis, but use of the filter significantly reduces memory requirements and CPU time for such analyses. We demonstrate the utility of the filter for urinary metabolite profiling using direct infusion electrospray ionization and a 15 tesla FTICR mass spectrometer. Electronic supplementary material The online version of this article (doi:10.1007/s11306-010-0202-2) contains supplementary material, which is available to authorized users. PMID:20676216

  14. Molecular resolution and fragmentation of fulvic acid by electrospray ionization/multistage tandem mass spectrometry

    Science.gov (United States)

    Leenheer, J.A.; Rostad, C.E.; Gates, Paul M.; Furlong, E.T.; Ferrer, I.

    2001-01-01

    Molecular weight distributions of fulvic acid from the Suwannee River, Georgia, were investigated by electrospray ionization/quadrupole mass spectrometry (ESI/QMS), and fragmentation pathways of specific fulvic acid masses were investigated by electrospray ionization/ion trap multistage tandem mass spectrometry (ESI/MST/MS). ESI/QMS studies of the free acid form of low molecular weight poly(carboxylic acid) standards in 75% methanol/25% water mobile phase found that negative ion detection gave the optimum generation of parent ions that can be used for molecular weight determinations. However, experiments with poly(acrylic acid) mixtures and specific high molecular weight standards found multiply charged negative ions that gave a low bias to molecular mass distributions. The number of negative charges on a molecule is dependent on the distance between charges. ESI/MST/MS of model compounds found characteristic water loss from alcohol dehydration and anhydride formation, as well as CO2 loss from decarboxylation, and CO loss from ester structures. Application of these fragmentation pathways to specific masses of fulvic acid isolated and fragmented by ESI/MST/MS is indicative of specific structures that can serve as a basis for future structural confirmation after these hypothesized structures are synthesized.

  15. Mobile high-resolution time-of-flight mass spectrometer for in-situ analytics

    Energy Technology Data Exchange (ETDEWEB)

    Lang, Johannes; Ebert, Jens [II. Physikalisches Institut, JLU, Giessen (Germany); Dickel, Timo; Geissel, Hans; Plass, Wolfgang; Scheidenberger, Christoph [II. Physikalisches Institut, JLU, Giessen (Germany); GSI, Darmstadt (Germany)

    2011-07-01

    A compact multiple-reflection time-of-flight mass spectrometer (MR-TOF-MS) has been developed. For the first time it allows for mass measurements with a resolving power exceeding 100000 and sub ppm accuracy in a mobile device. Thus it allows to resolve isobars and enables to accurately determine the composition and structure of biomolecules. The MR-TOF-MS consists of an atmospheric pressure interface for DESI and REIMS, ion cooler, ion trap, time-of-flight analyzer, MCP detector and DAQ. Vacuum system components, power supplies as well as electronics are mounted together with the ion optical spectrometer parts on a single frame with a total volume of 0.8 m{sup 3}. Applications of the device within the AmbiProbe research program include in-situ mass spectrometry such as real-time tissue recognition in electrosurgery, identification of mycotoxins and analysis of soil samples for environmental studies.

  16. High-resolution MALDI mass spectrometry imaging of gallotannins and monoterpene glucosides in the root of Paeonia lactiflora

    DEFF Research Database (Denmark)

    Li, Bin; Bhandari, Dhaka Ram; Römpp, Andreas

    2016-01-01

    High-resolution atmospheric-pressure scanning microprobe matrix-assisted laser desorption/ionization mass spectrometry imaging (AP-SMALDI MSI) at 10 μm pixel size was performed to unravel the spatio-chemical distribution of major secondary metabolites in the root of Paeonia lactiflora. The spatial...... distributions of two major classes of bioactive components, gallotannins and monoterpene glucosides, were investigated and visualized at the cellular level in tissue sections of P. lactiflora roots. Accordingly, other primary and secondary metabolites were imaged, including amino acids, carbohydrates, lipids...

  17. Applying 'Sequential Windowed Acquisition of All Theoretical Fragment Ion Mass Spectra' (SWATH) for systematic toxicological analysis with liquid chromatography-high-resolution tandem mass spectrometry.

    Science.gov (United States)

    Arnhard, Kathrin; Gottschall, Anna; Pitterl, Florian; Oberacher, Herbert

    2015-01-01

    Liquid chromatography-tandem mass spectrometry (LC-MS/MS) has become an indispensable analytical technique in clinical and forensic toxicology for detection and identification of potentially toxic or harmful compounds. Particularly, non-target LC-MS/MS assays enable extensive and universal screening requested in systematic toxicological analysis. An integral part of the identification process is the generation of information-rich product ion spectra which can be searched against libraries of reference mass spectra. Usually, 'data-dependent acquisition' (DDA) strategies are applied for automated data acquisition. In this study, the 'data-independent acquisition' (DIA) method 'Sequential Windowed Acquisition of All Theoretical Fragment Ion Mass Spectra' (SWATH) was combined with LC-MS/MS on a quadrupole-quadrupole-time-of-flight (QqTOF) instrument for acquiring informative high-resolution tandem mass spectra. SWATH performs data-independent fragmentation of all precursor ions entering the mass spectrometer in 21m/z isolation windows. The whole m/z range of interest is covered by continuous stepping of the isolation window. This allows numerous repeat analyses of each window during the elution of a single chromatographic peak and results in a complete fragment ion map of the sample. Compounds and samples typically encountered in forensic casework were used to assess performance characteristics of LC-MS/MS with SWATH. Our experiments clearly revealed that SWATH is a sensitive and specific identification technique. SWATH is capable of identifying more compounds at lower concentration levels than DDA does. The dynamic range of SWATH was estimated to be three orders of magnitude. Furthermore, the >600,000 SWATH spectra matched led to only 408 incorrect calls (false positive rate = 0.06 %). Deconvolution of generated ion maps was found to be essential for unravelling the full identification power of LC-MS/MS with SWATH. With the available software, however, only semi

  18. Time-Resolved Molecular Characterization of Limonene/Ozone Aerosol using High-Resolution Electrospray Ionization Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Bateman, Adam P.; Nizkorodov, Serguei; Laskin, Julia; Laskin, Alexander

    2009-09-09

    Molecular composition of limonene/O3 secondary organic aerosol (SOA) was investigated using high-resolution electrospray ionization mass spectrometry (HR-ESI-MS) as a function of reaction time. SOA was generated by ozonation of D-limonene in a reaction chamber and sampled at different time intervals using a cascade impactor. The SOA samples were extracted into acetonitrile and analyzed using a HR-ESI-MS instrument with a resolving power of 100,000 (m/Δm). The resulting mass spectra provided detailed information about the extent of oxidation inferred from the O:C ratios, double bond equivalency (DBE) factors, and aromaticity indexes (AI) in hundreds of identified individual SOA species.

  19. Non-standard interactions and the resolution of ordering of neutrino masses at DUNE and other long baseline experiments

    CERN Document Server

    Masud, Mehedi

    2016-01-01

    In the era of precision neutrino physics, we study the influence of matter NSI on the question of neutrino mass ordering and its resolution. At long baseline experiments, since matter effects play a crucial role in addressing this very important question, it is timely to investigate how sub-leading effects due to NSI may affect and drastically alter inferences pertaining to this question. We demonstrate that the sensitivity to mass ordering gets significantly impacted due to NSI effects for various long baseline experiments including the upcoming long baseline experiment, Deep Underground Neutrino Experiment (DUNE). Finally we draw a comparison of DUNE, with the sensitivities offered by two of the current neutrino beam experiments NOvA and T2K.

  20. Broad Separation of Isomeric Lipids by High-Resolution Differential Ion Mobility Spectrometry with Tandem Mass Spectrometry

    Science.gov (United States)

    Bowman, Andrew P.; Abzalimov, Rinat R.; Shvartsburg, Alexandre A.

    2017-08-01

    Maturation of metabolomics has brought a deeper appreciation for the importance of isomeric identity of lipids to their biological role, mirroring that for proteoforms in proteomics. However, full characterization of the lipid isomerism has been thwarted by paucity of rapid and effective analytical tools. A novel approach is ion mobility spectrometry (IMS) and particularly differential or field asymmetric waveform IMS (FAIMS) at high electric fields, which is more orthogonal to mass spectrometry. Here we broadly explore the power of FAIMS to separate lipid isomers, and find a 75% success rate across the four major types of glycero- and phospho- lipids ( sn, chain length, double bond position, and cis/ trans). The resolved isomers were identified using standards, and (for the first two types) tandem mass spectrometry. These results demonstrate the general merit of incorporating high-resolution FAIMS into lipidomic analyses.

  1. Methods for Identification of CA125 from Ovarian Cancer Ascites by High Resolution Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Florian Weiland

    2012-08-01

    Full Text Available CA125 is the most widely used tumour marker in ovarian cancer with unsatisfactory sensitivity and specificity especially at early stage. It is quantified by antibody-based immunoassays; however different molecular weight isoforms have been described in the literature which have never been validated by mass spectrometry, potentially affecting the diagnostic accuracy and clinical reliability of the test. In this study, CA125 was detected by Western blot and its identity confirmed by mass spectrometry. Two-dimensional (2D gel electrophoresis in combination with mass spectrometry revealed that positive Western blot signals up to 500 kDa are most likely false-positive interactions of M11-like and OC125-like antibodies. Fibronectin, identified as one of these false-positive interaction partners, increased the reading for CA125 in a first generation ELISA significantly (p = 0.02. The existence of low-molecular weight isoforms of CA125 is therefore questionable and is most likely reflecting cross-reactivity of the antibodies with other proteins. This would explain the conflicting reports on the molecular structure of CA125 and also the inconsistency of CA125 levels by different ELISAs. Our results are also the first steps towards a mass spectrometric assay for CA125 quantification, which would improve sensitivity and reliability.

  2. ION COMPOSITION ELUCIDATION (ICE): A HIGH RESOLUTION MASS SPECTROMETRIC TECHNIQUE FOR IDENTIFYING COMPOUNDS IN COMPLEX MIXTURES

    Science.gov (United States)

    When tentatively identifying compounds in complex mixtures using mass spectral libraries, multiple matches or no plausible matches due to a high level of chemical noise or interferences can occur. Worse yet, most analytes are not in the libraries. In each case, Ion Composition El...

  3. Molecular characterization of dissolved organic matter through a desalination process by high resolution mass spectrometry.

    Science.gov (United States)

    Cortés-Francisco, Nuria; Caixach, Josep

    2013-09-01

    The effect of different water treatments such as ultrafiltration (UF) and reverse osmosis (RO) on dissolved organic matter (DOM) is still unknown. Electrospray ionization Fourier transform orbitrap mass spectrometry has been used to provide valuable information of marine DOM evolution through a desalination process on a molecular scale. In the present manuscript, the characterization of four real composite water samples from a desalination pilot plant installed in the coast of Barcelona (Spain) has been carried out. The sampling was performed on each point of the pilot plant: raw seawater (RSW), UF effluent, brine RO and permeate RO. The mass spectra of the different samples show several thousand peaks, however for the present screening study, only the mass range m/z 200-500 and the main signals in this mass range (relative intensities ≥1%) have been considered. The analysis of RSW and UF samples reveal that there is little effect on DOM by the UF pilot. However, when the water is treated on the RO an important change on DOM has been observed. The recurring periodical patterns found in RSW and UF are lost in Permeate RO sample. Compounds with more aliphatic character, with higher H/C ratio (H/Cav 1.72) are present in the Permeate and some of them have been tentatively identified as fatty acids.

  4. The need for interval appendectomy after resolution of an appendiceal mass questioned

    NARCIS (Netherlands)

    Willemsen, PJ; Hoorntje, LE; Eddes, EH; Ploeg, RJ

    2002-01-01

    Background. Our current treatment of an appendiceal mass is initially conservative, followed by an interval appendectomy. The necessity of this routine interval appendectomy is debatable. A study was conducted to evaluate whether surgical factors and pathological features of the excised appendices s

  5. Accelerating resolution-of-the-identity second-order Møller-Plesset quantum chemistry calculations with graphical processing units.

    Science.gov (United States)

    Vogt, Leslie; Olivares-Amaya, Roberto; Kermes, Sean; Shao, Yihan; Amador-Bedolla, Carlos; Aspuru-Guzik, Alan

    2008-03-13

    The modification of a general purpose code for quantum mechanical calculations of molecular properties (Q-Chem) to use a graphical processing unit (GPU) is reported. A 4.3x speedup of the resolution-of-the-identity second-order Møller-Plesset perturbation theory (RI-MP2) execution time is observed in single point energy calculations of linear alkanes. The code modification is accomplished using the compute unified basic linear algebra subprograms (CUBLAS) library for an NVIDIA Quadro FX 5600 graphics card. Furthermore, speedups of other matrix algebra based electronic structure calculations are anticipated as a result of using a similar approach.

  6. Chemical composition, sources, and processes of urban aerosols during summertime in Northwest China: insights from High Resolution Aerosol Mass Spectrometry

    Science.gov (United States)

    Xu, J.; Zhang, Q.; Chen, M.; Ge, X.; Ren, J.; Qin, D.

    2014-06-01

    An aerodyne High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) was deployed along with a Scanning Mobility Particle Sizer (SMPS) and a Multi Angle Absorption Photometers (MAAP) to measure the temporal variations of the mass loading, chemical composition, and size distribution of sub-micrometer particulate matter (PM1) in Lanzhou, northwest China, during 12 July-7 August 2012. The average PM1 mass concentration including non-refractory PM1 (NR-PM1) measured by HR-ToF-AMS and black carbon (BC) measured by MAAP during this study was 24.5 μg m-3 (ranging from 0.86 to 105μg m-3), with a mean composition consisting of 47% organics, 16% sulfate, 12% BC, 11% ammonium, 10% nitrate, and 4% chloride. The organics was consisted of 70% carbon, 21% oxygen, 8% hydrogen, and 1% nitrogen, with the average oxygen-to-carbon ratio (O / C) of 0.33 and organic mass-to-carbon ratio (OM / OC) of 1.58. Positive matrix factorization (PMF) of the high-resolution mass spectra of organic aerosols (OA) identified four distinct factors which represent, respectively, two primary OA (POA) emission sources (traffic and food cooking) and two secondary OA (SOA) types - a fresher, semi-volatile oxygenated OA (SV-OOA) and a more aged, low-volatility oxygenated OA (LV-OOA). Traffic-related hydrocarbon-like OA (HOA) and BC displayed distinct diurnal patterns both with peak at ~07:00-11:00 (BJT: UTC +8) corresponding to the morning rush hours, while cooking OA (COA) peaked during three meal periods. The diurnal profiles of sulfate and LV-OOA displayed a broad peak between ∼07:00-15:00, while those of nitrate, ammonium, and SV-OOA showed a narrower peak at ~08:00-13:00. The later morning and early afternoon peak in the diurnal profiles of secondary aerosol species was likely caused by mixing down of pollutants aloft, which were likely produced in the residual layer decoupled from the boundary layer during night time. The mass spectrum of SV-OOA also showed similarity with that of

  7. Aerosol Organic Matter-Trace Metal Relationships Revealed by Ultra-High Resolution Mass Spectrometry

    Science.gov (United States)

    Wozniak, A. S.; Sleighter, R. L.; Morton, P. L.; Landing, W. M.; Shelley, R. U.; Hatcher, P. G.

    2011-12-01

    Atmospheric delivery of aerosols is important for the biogeochemical cycling of organic matter (OM) and trace elements in marine environments. Aerosols over marine environments can be derived from marine sources or transported from continental regions of variable vegetative cover and anthropogenic influence. These different sources are key determinants of aerosol OM composition, as well as trace metal amounts and characteristics. Dust-influenced aerosols typically contain higher amounts of Fe than anthropogenic-influenced aerosols but have lesser % of soluble Fe (%FeS), believed to be the bioavailable form of Fe for marine phytoplankton. Four samples from the 2008 GEOTRACES intercalibration experiments (Miami, FL, USA) were analyzed by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and related to both air mass back trajectories and %FeS. Three samples showed aerosol sources from the east consistent with Saharan dust inputs, while the fourth sample was derived in part from air masses to the north, influenced by the North American continent. This North American-influenced sample was collected following the 3 day period with the highest %FeS (1.3-1.7%) of the 11 day intercalibration experiment (mean = 0.4-1.1%). FT-ICR mass spectra showed 795 peaks common to the dust-influenced samples but absent from the North American-influenced sample. These peaks were assigned molecular formulas characterized by CHO and CHON compounds with lower H/C and O/C ratios than the 1257 formulas common to all 4 samples, suggesting that the dust-influenced aerosols carry OM that is less oxygenated and more condensed in structure along with Fe of lesser solubility. Air mass trajectory analyses revealed samples collected during a 2010 cruise in the North Atlantic Ocean to be characterized by European-influenced (anthropogenic), African-influenced (dust), and primarily marine air masses, making them ideal for further exploration of the

  8. High-Resolution Electrospray Ionization Mass Spectrometry Analysis of Water- Soluble Organic Aerosols Collected with a Particle into Liquid Sampler

    Energy Technology Data Exchange (ETDEWEB)

    Bateman, Adam P.; Nizkorodov, Serguei; Laskin, Julia; Laskin, Alexander

    2010-10-01

    This work demonstrates the utility of a particle-into-liquid sampler (PILS) a technique traditionally used for identification of inorganic ions present in ambient or laboratory aerosols for the analysis of water soluble organic aerosol (OA) using high resolution electrospray ionization mass spectrometry (HR ESI-MS). Secondary organic aerosol (SOA) was produced from 0.5 ppm mixing ratios of limonene and ozone in a 5 m3 Teflon chamber. SOA was collected simultaneously using a traditional filter sampler and a PILS. The filter samples were later extracted with either water or acetonitrile, while the aqueous PILS samples were analyzed directly. In terms of peak intensities, types of detectable compounds, average O:C ratios, and organic mass to organic carbon ratios, the resulting high resolution mass spectra were essentially identical for the PILS and filter based samples. SOA compounds extracted from both filter/acetonitrile extraction and PILS/water extraction accounted for >95% of the total ion current in ESI mass spectra. This similarity was attributed to high solubility of limonene SOA in water. In contrast, significant differences in detected ions and peak abundances were observed for pine needle biomass burning organic aerosol (BBOA) collected with PILS and filter sampling. The water soluble fraction of BBOA is considerably smaller than for SOA, and a number of unique peaks were detectable only by the filter/acetonitrile method. The combination of PILS collection with HR-ESI-MS analysis offers a new approach for molecular analysis of the water-soluble organic fraction in biogenic SOA, aged photochemical smog, and BBOA.

  9. Fast high-resolution computer-generated hologram computation using multiple graphics processing unit cluster system.

    Science.gov (United States)

    Takada, Naoki; Shimobaba, Tomoyoshi; Nakayama, Hirotaka; Shiraki, Atsushi; Okada, Naohisa; Oikawa, Minoru; Masuda, Nobuyuki; Ito, Tomoyoshi

    2012-10-20

    To overcome the computational complexity of a computer-generated hologram (CGH), we implement an optimized CGH computation in our multi-graphics processing unit cluster system. Our system can calculate a CGH of 6,400×3,072 pixels from a three-dimensional (3D) object composed of 2,048 points in 55 ms. Furthermore, in the case of a 3D object composed of 4096 points, our system is 553 times faster than a conventional central processing unit (using eight threads).

  10. [Variations in the diagnostic confirmation process between breast cancer mass screening units].

    Science.gov (United States)

    Natal, Carmen; Fernández-Somoano, Ana; Torá-Rocamora, Isabel; Tardón, Adonina; Castells, Xavier

    2016-01-01

    To analyse variations in the diagnostic confirmation process between screening units, variations in the outcome of each episode and the relationship between the use of the different diagnostic confirmation tests and the lesion detection rate. Observational study of variability of the standardised use of diagnostic and lesion detection tests in 34 breast cancer mass screening units participating in early-detection programmes in three Spanish regions from 2002-2011. The diagnostic test variation ratio in percentiles 25-75 ranged from 1.68 (further appointments) to 3.39 (fine-needle aspiration). The variation ratio in detection rates of benign lesions, ductal carcinoma in situ and invasive cancer were 2.79, 1.99 and 1.36, respectively. A positive relationship between rates of testing and detection rates was found with fine-needle aspiration-benign lesions (R(2): 0.53), fine-needle aspiration-invasive carcinoma (R(2): 0 28), core biopsy-benign lesions (R(2): 0.64), core biopsy-ductal carcinoma in situ (R(2): 0.61) and core biopsy-invasive carcinoma (R(2): 0.48). Variation in the use of invasive tests between the breast cancer screening units participating in early-detection programmes was found to be significantly higher than variations in lesion detection. Units which conducted more fine-needle aspiration tests had higher benign lesion detection rates, while units that conducted more core biopsies detected more benign lesions and cancer. Copyright © 2016 SESPAS. Published by Elsevier Espana. All rights reserved.

  11. Identification of codon-specific serine to asparagine mistranslation in recombinant monoclonal antibodies by high-resolution mass spectrometry.

    Science.gov (United States)

    Yu, X Christopher; Borisov, Oleg V; Alvarez, Melissa; Michels, David A; Wang, Yajun Jennifer; Ling, Victor

    2009-11-15

    Translation errors in protein biosynthesis may result in low level amino acid misincorporation and contribute to product heterogeneity of recombinant protein therapeutics. We report the use of peptide map analysis by reversed-phase high-performance liquid chromatography and high-resolution mass spectrometry to detect and identify mistranslation events in recombinant monoclonal antibodies expressed in mammalian cell lines including Chinese hamster ovary (CHO) cells. Misincorporation of an asparagine residue at multiple serine positions was detected as earlier-eluting peptides with masses 27.01 Da higher than expected. The exact positions at which misincorporation occurred were identified by tandem mass spectrometry of the asparagine-containing variant peptides. The identified asparagine misincorporation sites correlated with the use of codon AGC but with none of the other five serine codons. The relative levels of misincorporation ranged from 0.01%-0.2% among multiple serine positions detected across three different antibodies by targeted analysis of expected and variant peptides. The low levels of misincorporation are consistent with published predictions for in vivo translation error rates. Our results demonstrate that state-of-the-art mass spectrometry with a combination of high sensitivity, accuracy, and dynamic range provides a new ability to discover and characterize low level protein variants that arise from mistranslation events.

  12. Dereplication of known nucleobase and nucleoside compounds in natural product extracts by capillary electrophoresis-high resolution mass spectrometry.

    Science.gov (United States)

    Chen, Junhui; Shi, Qian; Wang, Yanlong; Li, Zhaoyong; Wang, Shuai

    2015-03-26

    Nucleobase and nucleoside compounds exist widely in various organisms. An often occurring problem in the discovery of new bioactive compounds from natural products is reisolation of known nucleobase and nucleoside compounds. To resolve this problem, a capillary electrophoresis-high resolution mass spectrometry (CE-HR-MS) method providing both rapid separation and accurate mass full-scan MS data was developed for the first time to screen and dereplicate known nucleobase and nucleoside compounds in crude extracts of natural products. Instrumental parameters were optimized to obtain optimum conditions for CE separation and electrospray ionization-time-of-flight mass spectrometry (ESI-TOF/MS) detection. The proposed method was verified to be precise, reproducible, and sensitive. Using this method, known nucleobase and nucleoside compounds in different marine medicinal organisms including Syngnathus acus Linnaeus; Hippocampus japonicus Kaup and Anthopleura lanthogrammica Berkly were successfully observed and identified. This work demonstrates that CE-HR-MS combined with an accurate mass database may be used as a powerful tool for dereplicating known nucleobase and nucleoside compounds in different types of natural products. Rapid dereplication of known nucleobase and nucleoside compounds allows researchers to focus on other leads with greater potential to yield new substances.

  13. Dereplication of Known Nucleobase and Nucleoside Compounds in Natural Product Extracts by Capillary Electrophoresis-High Resolution Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Junhui Chen

    2015-03-01

    Full Text Available Nucleobase and nucleoside compounds exist widely in various organisms. An often occurring problem in the discovery of new bioactive compounds from natural products is reisolation of known nucleobase and nucleoside compounds. To resolve this problem, a capillary electrophoresis-high resolution mass spectrometry (CE-HR-MS method providing both rapid separation and accurate mass full-scan MS data was developed for the first time to screen and dereplicate known nucleobase and nucleoside compounds in crude extracts of natural products. Instrumental parameters were optimized to obtain optimum conditions for CE separation and electrospray ionization-time-of-flight mass spectrometry (ESI-TOF/MS detection. The proposed method was verified to be precise, reproducible, and sensitive. Using this method, known nucleobase and nucleoside compounds in different marine medicinal organisms including Syngnathus acus Linnaeus; Hippocampus japonicus Kaup and Anthopleura lanthogrammica Berkly were successfully observed and identified. This work demonstrates that CE-HR-MS combined with an accurate mass database may be used as a powerful tool for dereplicating known nucleobase and nucleoside compounds in different types of natural products. Rapid dereplication of known nucleobase and nucleoside compounds allows researchers to focus on other leads with greater potential to yield new substances.

  14. Geomorphology of Late Quaternary Mass Movement Deposits using a Decimetre-Resolution 3D Seismic Volume: Case Studies from Windermere, UK, and Trondheimsfjorden, Norway

    Science.gov (United States)

    Vardy, M. E.; Dix, J. K.; Henstock, T.; Bull, J. M.; Pinson, L.; L'Heureux, J.; Longva, O.; Hansen, L.; Chand, S.; Gutowski, M.

    2009-12-01

    We present results from decimetre resolution 3D seismic volumes acquired over Late Quaternary mass movement deposits in both Lake Windermere, UK, and the Trondheim Harbour area, central Norway. Both deposits were imaged using the 3D Chirp sub-bottom profiler, which combines the known, highly repeatable source waveform of Chirp profilers with the coherent processing and interpretation afforded by true 3D seismic volumes. Reflector morphology from these two volumes are used to identify and map structure on scales of 10s cm to 100s metres. This shows the applicability of the method for the interpretation of failure mechanism, flow morphology and depositional style in these two environments. In Windermere, Younger Dryas deposits have been substantially reworked by the episodic redistribution of sediment from the steep lakesides into the basin. Within the 100 x 400 m 3D seismic volume we identify two small debris flow deposits (1500 m3 and 60,000 m3) and one large (500,000 m3) erosive mass flow deposit. These two depositional mechanisms are distinct. The debris flows have high amplitude, chaotic internal reflections, with a high amplitude reflector representing a lower erosional boundary, discontinuous low amplitude top reflector, and thin out rapidly with distance from the lake margin. The thicker mass flow unit lacks internal structure, and has high amplitude top and base reflectors,. In the Trondheim Harbour we image the down-slope extent of three large slide blocks (which have a net volume > 1 x 106 m3), mobilised by a landslide in 1990, in the 100 x 450 m 3D seismic volume. The morphology of these mass movement deposits is distinct again; demonstrating translational failure along a clear slip plane, leaving well defined slide scars, and forming prominent compressional/extensional structures.

  15. Impact of model resolution on simulated wind, drifting snow and surface mass balance in Terre Adélie, East Antarctica

    NARCIS (Netherlands)

    Lenaerts, J.T.M.; van den Broeke, M.R.; Scarchilli, C.; Agosta, C.

    2012-01-01

    This paper presents the impact of model resolution on the simulated wind speed, drifting snow climate and surface mass balance (SMB) of Terre Ad´elie and its surroundings, East Antarctica. We compare regional climate model simulations at 27 and 5.5 km resolution for the year 2009. The wind speed max

  16. Retrieval of Precise Radial Velocities from Near-Infrared High Resolution Spectra of Low Mass Stars

    CERN Document Server

    Gao, Peter; Gagné, Jonathan; Furlan, Elise; Bottom, Michael; Anglada-Escudé, Guillem; White, Russel; Davison, Cassy; Beichman, Charles; Brinkworth, Carolyn; Johnson, John; Ciardi, David; Wallace, James; Mennesson, Bertrand; von Braun, Kaspar; Vasisht, Gautam; Prato, Lisa; Kane, Stephen; Tanner, Angelle; Crawford, Timothy; Latham, David; Rougeot, Raphaël; Geneser, Claire; Catanzarite, Joseph

    2016-01-01

    Given that low-mass stars have intrinsically low luminosities at optical wavelengths and a propensity for stellar activity, it is advantageous for radial velocity (RV) surveys of these objects to use near-infrared (NIR) wavelengths. In this work we describe and test a novel RV extraction pipeline dedicated to retrieving RVs from low mass stars using NIR spectra taken by the CSHELL spectrograph at the NASA Infrared Telescope Facility, where a methane isotopologue gas cell is used for wavelength calibration. The pipeline minimizes the residuals between the observations and a spectral model composed of templates for the target star, the gas cell, and atmospheric telluric absorption; models of the line spread function, continuum curvature, and sinusoidal fringing; and a parameterization of the wavelength solution. The stellar template is derived iteratively from the science observations themselves without a need for separate observations dedicated to retrieving it. Despite limitations from CSHELL's narrow wavelen...

  17. High resolution fossil fuel combustion CO2 emission fluxes for the United States.

    Science.gov (United States)

    Gurney, Kevin R; Mendoza, Daniel L; Zhou, Yuyu; Fischer, Marc L; Miller, Chris C; Geethakumar, Sarath; de la Rue du Can, Stephane

    2009-07-15

    Quantification of fossil fuel CO2 emissions at fine space and time resolution is emerging as a critical need in carbon cycle and climate change research. As atmospheric CO2 measurements expand with the advent of a dedicated remote sensing platform and denser in situ measurements, the ability to close the carbon budget at spatial scales of approximately 100 km2 and daily time scales requires fossil fuel CO2 inventories at commensurate resolution. Additionally, the growing interest in U.S. climate change policy measures are best served by emissions that are tied to the driving processes in space and time. Here we introduce a high resolution data product (the "Vulcan" inventory: www.purdue.edu/eas/carbon/vulcan/) that has quantified fossil fuel CO2 emissions for the contiguous U.S. at spatial scales less than 100 km2 and temporal scales as small as hours. This data product completed for the year 2002, includes detail on combustion technology and 48 fuel types through all sectors of the U.S. economy. The Vulcan inventory is built from the decades of local/regional air pollution monitoring and complements these data with census, traffic, and digital road data sets. The Vulcan inventory shows excellent agreement with national-level Department of Energy inventories, despite the different approach taken by the DOE to quantify U.S. fossil fuel CO2 emissions. Comparison to the global 1degree x 1 degree fossil fuel CO2 inventory, used widely by the carbon cycle and climate change community prior to the construction of the Vulcan inventory, highlights the space/time biases inherent in the population-based approach.

  18. High resolution fossil fuel combustion CO2 emission fluxes for the United States

    Energy Technology Data Exchange (ETDEWEB)

    Gurney, Kevin R.; Mendoza, Daniel L.; Zhou, Yuyu; Fischer, Marc L.; Miller, Chris C.; Geethakumar, Sarath; de la Rue du Can, Stephane

    2009-03-19

    Quantification of fossil fuel CO{sub 2} emissions at fine space and time resolution is emerging as a critical need in carbon cycle and climate change research. As atmospheric CO{sub 2} measurements expand with the advent of a dedicated remote sensing platform and denser in situ measurements, the ability to close the carbon budget at spatial scales of {approx}100 km{sup 2} and daily time scales requires fossil fuel CO{sub 2} inventories at commensurate resolution. Additionally, the growing interest in U.S. climate change policy measures are best served by emissions that are tied to the driving processes in space and time. Here we introduce a high resolution data product (the 'Vulcan' inventory: www.purdue.edu/eas/carbon/vulcan/) that has quantified fossil fuel CO{sub 2} emissions for the contiguous U.S. at spatial scales less than 100 km{sup 2} and temporal scales as small as hours. This data product, completed for the year 2002, includes detail on combustion technology and 48 fuel types through all sectors of the U.S. economy. The Vulcan inventory is built from the decades of local/regional air pollution monitoring and complements these data with census, traffic, and digital road data sets. The Vulcan inventory shows excellent agreement with national-level Department of Energy inventories, despite the different approach taken by the DOE to quantify U.S. fossil fuel CO{sub 2} emissions. Comparison to the global 1{sup o} x 1{sup o} fossil fuel CO{sub 2} inventory, used widely by the carbon cycle and climate change community prior to the construction of the Vulcan inventory, highlights the space/time biases inherent in the population-based approach.

  19. On the conversion of tritium units to mass fractions for hydrologic applications

    Science.gov (United States)

    Stonestrom, David A.; Andraski, Brain J.; Cooper, Clay A.; Mayers, Charles J.; Michel, Robert L.

    2013-01-01

    We develop a general equation for converting laboratory-reported tritium levels, expressed either as concentrations (tritium isotope number fractions) or mass-based specific activities, to mass fractions in aqueous systems. Assuming that all tritium is in the form of monotritiated water simplifies the derivation and is shown to be reasonable for most environmental settings encountered in practice. The general equation is nonlinear. For tritium concentrations c less than 4.5×1012 tritium units (TU) - i.e. specific tritium activities11 Bq kg-1 - the mass fraction w of tritiated water is approximated to within 1 part per million by w ≈ c×2.22293×10-18, i.e. the conversion is linear for all practical purposes. Terrestrial abundances serve as a proxy for non-tritium isotopes in the absence of sample-specific data. Variation in the relative abundances of non-tritium isotopes in the terrestrial hydrosphere produces a minimum range for the mantissa of the conversion factor of [2.22287; 2.22300].

  20. Mass flow-rate control unit to calibrate hot-wire sensors

    Energy Technology Data Exchange (ETDEWEB)

    Durst, F.; Uensal, B. [FMP Technology GmbH, Erlangen (Germany); Haddad, K. [FMP Technology GmbH, Erlangen (Germany); Friedrich-Alexander-Universitaet Erlangen-Nuernberg, LSTM-Erlangen, Institute of Fluid Mechanics, Erlangen (Germany); Al-Salaymeh, A.; Eid, Shadi [University of Jordan, Mechanical Engineering Department, Faculty of Engineering and Technology, Amman (Jordan)

    2008-02-15

    Hot-wire anemometry is a measuring technique that is widely employed in fluid mechanics research to study the velocity fields of gas flows. It is general practice to calibrate hot-wire sensors against velocity. Calibrations are usually carried out under atmospheric pressure conditions and these suggest that the wire is sensitive to the instantaneous local volume flow rate. It is pointed out, however, that hot wires are sensitive to the instantaneous local mass flow rate and, of course, also to the gas heat conductivity. To calibrate hot wires with respect to mass flow rates per unit area, i.e., with respect to ({rho}U), requires special calibration test rigs. Such a device is described and its application is summarized within the ({rho}U) range 0.1-25 kg/m{sup 2} s. Calibrations are shown to yield the same hot-wire response curves for density variations in the range 1-7 kg/m{sup 3}. The application of the calibrated wires to measure pulsating mass flows is demonstrated, and suggestions are made for carrying out extensive calibrations to yield the ({rho}U) wire response as a basis for advanced fluid mechanics research on ({rho}U) data in density-varying flows. (orig.)

  1. Quantification of Trace Amounts of Impurities in High Purity Cobalt by High Resolution Inductively Coupled Plasma Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    Hua Lin XIE; Xi Du NIE; You Gen TANG

    2006-01-01

    An analytical method using high resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) for rapid simultaneous determination of Be, Mg, Al, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Ge, As, Se, Mo, Ag, Cd, Sn, Sb, Ba, Pt, Au and Pb in high purity cobalt was described. Sample digestions were performed in closed microwave vessels using HNO3 and HCl. The matrix effects due to thc presence of excess HCl and Co were evaluated. The usefulness of high mass resolution for overcoming some spectral interference was demonstrated. The optimum conditions for the determination was tested and discussed. Correction for matrix effects, Sc, Rh and Bi were used as internal standards. The detection limits is 0.003-0.57 μg/g, the recovery ratio is 92.2%- 111.2%, and the RSD is less than 3.6%. The method is accurate, quick and convenient. It has been applied to the determination of trace impurities in high purity cobalt with satisfactory results.

  2. Quantification of trace amounts of impurities in high purity cobalt by high resolution inductively coupled plasma mass spectrometry

    Institute of Scientific and Technical Information of China (English)

    XIE Hualin; HUANG Kelong; NIE Xidu; TANG Yougen

    2007-01-01

    An analytical method using high resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) for rapid simultaneous determination of 24 elements (Be, Mg, Al, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Ge, As, Se, Mo, Ag, Cd, Sn,Sb, Ba, Pt, Au, and Pb) in high purity cobalt was described. Sample digestions were performed in closed microwave vessels using HNO3 and HCl. The matrix effects because of the presence of excess HCl and Co were evaluated. The usefulness of high mass resolution for overcoming some spectral interference was demonstrated. The optimum conditions for the determination were tested and discussed. The standard addition method was employed for quantitative analysis. The detection limits were 0.016-1.50 μg.g-1, the recovery ratios were 92.2%-111.2%, and the RSD was less than 3.6%. The method was accurate, quick, and convenient. It was applied to the determination of trace impurities in high purity cobalt with satisfactory results.

  3. Phase I and phase II reductive metabolism simulation of nitro aromatic xenobiotics with electrochemistry coupled with high resolution mass spectrometry.

    Science.gov (United States)

    Bussy, Ugo; Chung-Davidson, Yu-Wen; Li, Ke; Li, Weiming

    2014-11-01

    Electrochemistry combined with (liquid chromatography) high resolution mass spectrometry was used to simulate the general reductive metabolism of three biologically important nitro aromatic molecules: 3-trifluoromethyl-4-nitrophenol (TFM), niclosamide, and nilutamide. TFM is a pesticide used in the Laurential Great Lakes while niclosamide and nilutamide are used in cancer therapy. At first, a flow-through electrochemical cell was directly connected to a high resolution mass spectrometer to evaluate the ability of electrochemistry to produce the main reduction metabolites of nitro aromatic, nitroso, hydroxylamine, and amine functional groups. Electrochemical experiments were then carried out at a constant potential of -2.5 V before analysis of the reduction products by LC-HRMS, which confirmed the presence of the nitroso, hydroxylamine, and amine species as well as dimers. Dimer identification illustrates the reactivity of the nitroso species with amine and hydroxylamine species. To investigate xenobiotic metabolism, the reactivity of nitroso species to biomolecules was also examined. Binding of the nitroso metabolite to glutathione was demonstrated by the observation of adducts by LC-ESI(+)-HRMS and the characteristics of their MSMS fragmentation. In conclusion, electrochemistry produces the main reductive metabolites of nitro aromatics and supports the observation of nitroso reactivity through dimer or glutathione adduct formation.

  4. Preprocessing significantly improves the peptide/protein identification sensitivity of high-resolution isobarically labeled tandem mass spectrometry data.

    Science.gov (United States)

    Sheng, Quanhu; Li, Rongxia; Dai, Jie; Li, Qingrun; Su, Zhiduan; Guo, Yan; Li, Chen; Shyr, Yu; Zeng, Rong

    2015-02-01

    Isobaric labeling techniques coupled with high-resolution mass spectrometry have been widely employed in proteomic workflows requiring relative quantification. For each high-resolution tandem mass spectrum (MS/MS), isobaric labeling techniques can be used not only to quantify the peptide from different samples by reporter ions, but also to identify the peptide it is derived from. Because the ions related to isobaric labeling may act as noise in database searching, the MS/MS spectrum should be preprocessed before peptide or protein identification. In this article, we demonstrate that there are a lot of high-frequency, high-abundance isobaric related ions in the MS/MS spectrum, and removing isobaric related ions combined with deisotoping and deconvolution in MS/MS preprocessing procedures significantly improves the peptide/protein identification sensitivity. The user-friendly software package TurboRaw2MGF (v2.0) has been implemented for converting raw TIC data files to mascot generic format files and can be downloaded for free from https://github.com/shengqh/RCPA.Tools/releases as part of the software suite ProteomicsTools. The data have been deposited to the ProteomeXchange with identifier PXD000994.

  5. Ice Mass Changes in the Russian High Arctic from Repeat High Resolution Topography.

    Science.gov (United States)

    Willis, Michael; Zheng, Whyjay; Pritchard, Matthew; Melkonian, Andrew; Morin, Paul; Porter, Claire; Howat, Ian; Noh, Myoung-Jong; Jeong, Seongsu

    2016-04-01

    We use a combination of ASTER and cartographically derived Digital Elevation Models (DEMs) supplemented with WorldView DEMs, the ArcticDEM and ICESat lidar returns to produce a time-series of ice changes occurring in the Russian High Arctic between the mid-20th century and the present. Glaciers on the western, Barents Sea coast of Novaya Zemlya are in a state of general retreat and thinning, while those on the eastern, Kara Sea coast are retreating at a slower rate. Franz Josef Land has a complicated pattern of thinning and thickening, although almost all the thinning is associated with rapid outlet glaciers feeding ice shelves. Severnaya Zemlya is also thinning in a complicated manner. A very rapid surging glacier is transferring mass into the ocean from the western periphery of the Vavilov Ice Cap on October Revolution Island, while glaciers feeding the former Matusevich Ice Shelf continue to thin at rates that are faster than those observed during the operational period of ICESat, between 2003 and 2009. Passive microwave studies indicate the total number of melt days is increasing in the Russian Arctic, although much of the melt may refreeze within the firn. It is likely that ice dynamic changes will drive mass loss for the immediate future. The sub-marine basins beneath several of the ice caps in the region suggest the possibility that mass loss rates may accelerate in the future.

  6. Matrix-assisted ionization vacuum for high-resolution Fourier transform ion cyclotron resonance mass spectrometers.

    Science.gov (United States)

    Wang, Beixi; Tisdale, Evgenia; Trimpin, Sarah; Wilkins, Charles L

    2014-07-15

    Matrix-assisted ionization vacuum (MAIV) produces charge states similar to electrospray ionization (ESI) from the solid state without requiring high voltage or added heat. MAIV differs from matrix-assisted laser desorption/ionization (MALDI) in that no laser is needed and abundant multiply charged ions are produced from molecules having multiple basic sites such as proteins. Here we introduce simple modifications to the commercial vacuum MALDI and ESI sources of a 9.4 T Fourier transform-ion cyclotron resonance (FT-ICR) mass spectrometer to perform MAIV from both intermediate and atmospheric pressure. The multiply charged ions are shown for the proteins bovine insulin, ubiquitin, and lysozyme using 3-nitrobenzonitrile as matrix. These are the first examples of MAIV operating at pressures as low as 10(-6) mbar in an FT-ICR mass spectrometer source, and the expected mass resolving power of 100000 to 400000 is achieved. Identical protein charge states are observed with and without laser ablation indicating minimal, if any, role of photochemical ionization for the compounds studied.

  7. Triacylglycerol profiling of microalgae strains for biofuel feedstock by liquid chromatography-high-resolution mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    MacDougall, Karen M.; McNichol, Jesse; McGinn, Patrick J.; O' Leary, Stephen J.B.; Melanson, Jeremy E. [Institute for Marine Biosciences, National Research Council of Canada, Halifax, NS (Canada)

    2011-11-15

    Biofuels from photosynthetic microalgae are quickly gaining interest as a viable carbon-neutral energy source. Typically, characterization of algal feedstock involves breaking down triacylglycerols (TAG) and other intact lipids, followed by derivatization of the fatty acids to fatty acid methyl esters prior to analysis by gas chromatography (GC). However, knowledge of the intact lipid profile could offer significant advantages for discovery stage biofuel research such as the selection of an algal strain or the optimization of growth and extraction conditions. Herein, lipid extracts from microalgae were directly analyzed by ultra-high pressure liquid chromatography-mass spectrometry (UHPLC-MS) using a benchtop Orbitrap mass spectrometer. Phospholipids, glycolipids, and TAGs were analyzed in the same chromatographic run, using a combination of accurate mass and diagnostic fragment ions for identification. Using this approach, greater than 100 unique TAGs were identified over the six algal strains studied and TAG profiles were obtained to assess their potential for biofuel applications. Under the growth conditions employed, Botryococcus braunii and Scenedesmus obliquus yielded the most comprehensive TAG profile with a high abundance of TAGs containing oleic acid. (orig.)

  8. Chemical characterization of particle emissions from controlled burns of biomass fuels using a high resolution time-of-flight aerosol mass spectrometer

    Science.gov (United States)

    Qi, L.; Hosseini, S.; Jung, H.; Yokelson, B.; Weise, D.; Cocker, D., III; Huang, Y.

    2012-03-01

    A total of forty-nine burns were conducted at the Missoula Fire Sciences Lab consisting of nine fuel types; i.e., chamise scrub oak, ceanothus, maritime chaparral, coastal sage scrub, California sage brush, Manzanita, oak savanna, oak woodland and masticated mesquite. This paper focuses on the chemical characterization of fine particle emissions collected for flaming, mixed and smoldering phases using a HR ToF-AMS. The evolution of OM/OC, H/C, O/C and N/C from fire ignition to extinction was measured to capture the transient and integrated chemical composition of the non-refractory portion of bulk particles. Real time elemental ratios and empirical formulas derived with respect to modified combustion efficiency (MCE) are reported. For each fuel, the hydrogen fragment ions dominate the unit mass resolution (UMR) mass spectra with no specific fragment ions attributable to an individual ecological combination. An interference ion in the UMR m/z 73, a fragment normally attributed to levoglucosan, is noted. Therefore, the results imply that C2H4O2+ (m/z 60.021) plus C3H5O2+ (m/z 73.029) are more sufficient to estimate the contribution of levoglucosan. The results did not show significant variations of levoglucosan content in the organic particle with the overall average contribution fraction ranging from 0.74% for coastal sage to 1.93% for chamise.

  9. Present and Future Surface Mass Budget of Small Arctic Ice Caps in a High Resolution Regional Climate Model

    Science.gov (United States)

    Mottram, Ruth; Langen, Peter; Koldtoft, Iben; Midefelt, Linnea; Hesselbjerg Christensen, Jens

    2016-04-01

    Globally, small ice caps and glaciers make a substantial contribution to sea level rise; this is also true in the Arctic. Around Greenland small ice caps are surprisingly important to the total mass balance from the island as their marginal coastal position means they receive a large amount of precipitation and also experience high surface melt rates. Since small ice caps and glaciers have had a disproportionate number of long-term monitoring and observational schemes in the Arctic, likely due to their relative accessibility, they can also be a valuable source of data. However, in climate models the surface mass balance contributions are often not distinguished from the main ice sheet and the presence of high relief topography is difficult to capture in coarse resolution climate models. At the same time, the diminutive size of marginal ice masses in comparison to the ice sheet makes modelling their ice dynamics difficult. Using observational data from the Devon Ice Cap in Arctic Canada and the Renland Ice Cap in Eastern Greenland, we assess the success of a very high resolution (~5km) regional climate model, HIRHAM5 in capturing the surface mass balance (SMB) of these small ice caps. The model is forced with ERA-Interim and we compare observed mean SMB and the interannual variability to assess model performance. The steep gradient in topography around Renland is challenging for climate models and additional statistical corrections are required to fit the calculated surface mass balance to the high relief topography. Results from a modelling experiment at Renland Ice Cap shows that this technique produces a better fit between modelled and observed surface topography. We apply this statistical relationship to modelled SMB on the Devon Ice Cap and use the long time series of observations from this glacier to evaluate the model and the smoothed SMB. Measured SMB values from a number of other small ice caps including Mittivakkat and A.P. Olsen ice cap are also compared

  10. DOTS: A High Resolution Orbitrap Mass Spectrometer for In Situ Analysis of the surface samples of Airless Planetary Bodies

    Science.gov (United States)

    Briois, Christelle; Thissen, Roland; Engrand, Cécile; Altwegg, Kathrin; Bouabdellah, Abdel; Boukrara, Amirouche; Carrasco, Nathalie; Chapuis, Claude; Cottin, Hervé; Grün, Eberhard; Grand, Noel; Henkel, Hartmut; Kempf, Sascha; Lebreton, Jean-Pierre; Makarov, Alexander A.; Postber, Frank; Srama, Ralf; Schmidt, Jürgen; Szopa, Cyril; Thirkell, Laurent; Tobie, Gabriel; Wurz, Peter; Zolotov, Mikhail Yu

    2013-04-01

    The dust detectors on board the Ulysses and Galileo spacecraft have shown that the Galilean satellites are surrounded by clouds of sub-micrometer size grains generated by impacts of interplanetary (micro-) meteoroids [1, 2]. In situ chemical analysis from orbit of these ballistic grains ejected from the surface of airless bodies provides a unique opportunity to remotely access the chemical composition of the Jovian moons' surface and subsurface. For Saturn, in situ identification by the Cassini Dust Analyzer (CDA) of sodium in icy grains in the E-Ring and in Enceladus plumes have proven a subsurface liquid water reservoir inside Enceladus [3, 4]. Noticeably, this was not accessible to other in situ or traditional remote sensing techniques. In situ measurements, either during a flyby or from orbit, of grains ejected from the surface, or emerging from the subsurface, of an airless body is a powerful tool to remotely study its surface composition and the nature of its geological activity. Crucial constraints on habitability can thus be determined. Our consortium of laboratories, in collaboration with Thermo Fischer Scientific [5, 6], is currently developing a high mass resolution Fourier Transform (FT) Orbitrap-based mass spectrometer optimized for in situ analysis of dust and icy grains in the environment of Solar System airless bodies. This new generation of dust mass spectrometer was studied in the framework of the Europa Jupiter System Mission (EJSM) instrument study in 2010-2012 and proposed in response to ESA's AO for the JUpiter ICy moons Explorer (JUICE) mission [7]. This mass analyser can provide very high mass resolution analysis (M/ΔM reaching 50 000 at m/z 50 Da). DOTS would allow identification of elemental and molecular species with excellent accuracy, in the 20-1000 Da mass range. In the context of the JUICE mission, DOTS would provide decisive information on the surface composition and on the putative liquid oceans in the subsurface of Ganymede

  11. [Chakrabarty today: 30 years after the United States Supreme Court Resolution].

    Science.gov (United States)

    Bergel, Salvador Darío

    2010-01-01

    The decision of the United States Supreme Court in the Chakrabarty case marked the beginning of a far reaching process, the development of which considerably extended the field of patentabiltiy of humans, their body parts and genetic information. The author believes that a period of three decades is sufficient to draw conclusions. A critical point has been reached from a debatable decision, which had more economic support than legal, which requires serious recapitulation of the scope and the purpose of industrial property rights.

  12. CORRELATION BETWEEN THE DAMPING FACTOR PER UNIT MASS AND THE FREE LENGTH FOR COMPOSITE SANDWICH BARS. EXPERIMENTAL INVESTIGATIONS

    Directory of Open Access Journals (Sweden)

    Cristian-Oliviu BURADA

    2015-05-01

    Full Text Available In this paper we have build some composite sandwich bars in this way: the core is made with polypropylene honeycomb (its thickness is 10, 15 and 20 mm reinforced with 1 layer of carbon fiber (on the sample upper and lower sides. For these samples we have determined, by experimental means, the damping factor per unit mass and per unit length. Then, by using the regression analysis, we have established correlations between the damping factor per unit mass and the bars free length. In order to obtain these correlations, we have considered the next free lengths of the bars: 200, 230, 260, 290, 320, 350.

  13. High-Resolution Live-Cell Imaging and Analysis by Laser Desorption/Ionization Droplet Delivery Mass Spectrometry.

    Science.gov (United States)

    Lee, Jae Kyoo; Jansson, Erik T; Nam, Hong Gil; Zare, Richard N

    2016-05-17

    We have developed a new ambient-ionization mass spectrometric technique named laser desorption/ionization droplet delivery mass spectrometry (LDIDD-MS). LDIDD-MS permits high-resolution, high-sensitivity imaging of tissue samples as well as measurements of both single-cell apoptosis and live-cell exocytosis. A pulsed (15 Hz) UV laser beam (266 nm) is focused on a surface covered with target analytes to trigger their desorption and ionization. A spray of liquid droplets is simultaneously directed onto the laser-focused surface region to capture the ionized analytes and deliver them to a mass spectrometer. The approach of rapid and effective capturing of molecules after laser desorption/ionization allows the limit of detection for the amino acid lysine to be as low as 2 amol under ambient ionization conditions. Two-dimensional maps of the desorbed/ionized species are recorded by moving the sample on an XY translational stage. The spatial resolution for imaging with LDIDD-MS was determined to be 2.4 μm for an ink-printed pattern and 3 μm for mouse brain tissue. We applied LDIDD-MS to single-cell analysis of apoptotic HEK cells. Differences were observed in the profiles of fatty acids and lipids between healthy HEK cells and those undergoing apoptosis. We observed upregulation of phosphatidylcholine (PC) with a relatively shorter carbon chain length and downregulation of PC with a relatively longer carbon chain length. We also applied LDIDD-MS for a real-time direct measurements of live-cell exocytosis. The catecholamine dopamine and trace amines (phenethylamine and tyramine) were detected from live PC12 cells without damaging them.

  14. Accurate proteome-wide protein quantification from high-resolution 15N mass spectra.

    Science.gov (United States)

    Khan, Zia; Amini, Sasan; Bloom, Joshua S; Ruse, Cristian; Caudy, Amy A; Kruglyak, Leonid; Singh, Mona; Perlman, David H; Tavazoie, Saeed

    2011-12-19

    In quantitative mass spectrometry-based proteomics, the metabolic incorporation of a single source of 15N-labeled nitrogen has many advantages over using stable isotope-labeled amino acids. However, the lack of a robust computational framework for analyzing the resulting spectra has impeded wide use of this approach. We have addressed this challenge by introducing a new computational methodology for analyzing 15N spectra in which quantification is integrated with identification. Application of this method to an Escherichia coli growth transition reveals significant improvement in quantification accuracy over previous methods.

  15. Site-specific glycosylation of donkey milk lactoferrin investigated by high-resolution mass spectrometry

    DEFF Research Database (Denmark)

    Gallina, Serafina; Saletti, Rosaria; Cunsolo, Vincenzo;

    2016-01-01

    A comprehensive monosaccharide composition of the N-glycans of donkey milk lactoferrin, isolated by ion exchange chromatography from an individual milk sample, was obtained by means of chymotryptic digestion, TiO2 and HILIC enrichment, reversed-phase high-performance liquid chromatography......, electrospray mass spectrometry, and high collision dissociation fragmentation. The results obtained allowed identifying 26 different glycan structures, including high mannose, complex and hybrid N-glycans, linked to the protein backbone via an amide bond to asparagine residues located at the positions 137, 281...

  16. Screening for exogenous androgen anabolic steroids in human hair by liquid chromatography/orbitrap-high resolution mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Strano-Rossi, Sabina, E-mail: sabina.stranorossi@rm.unicatt.it [Institute of Legal Medicine, Catholic University of Sacred Heart, L.go F. Vito, 1, 00168 Rome (Italy); Castrignanò, Erika; Anzillotti, Luca; Odoardi, Sara; De-Giorgio, Fabio [Institute of Legal Medicine, Catholic University of Sacred Heart, L.go F. Vito, 1, 00168 Rome (Italy); Bermejo, Ana [Institute of Legal Medicine, University of Santiago de Compostela, Av S. Francisco s/n, Santiago de Compostela (Spain); Pascali, Vincenzo L. [Institute of Legal Medicine, Catholic University of Sacred Heart, L.go F. Vito, 1, 00168 Rome (Italy)

    2013-09-02

    Graphical abstract: -- Highlights: •LC–HRMS screening method for the detection of a variety of anabolics in hair. •Detection of unmetabolized anabolic steroids and their esters in hair matrix by simple keratin pretreatment. •Identification of target compounds by retention time, accurate mass and isotopic cluster. •Quantitative determination of detected compounds. •Possibility to a retrospective re-analysis of the acquired datafile in case a further analyte is to be screened. -- Abstract: A method for the screening of various anabolic steroids and their esters in human hair, based on liquid-chromatography–high resolution mass spectrometry using an Exactive benchtop Orbitrap mass spectrometer, has been set up and validated. This method involved methanolic incubation of 30 mg of hair and analysis of the relevant extract in HPLC using a C18 column. The mass detector, with nominal resolving power of 100,000, operated in full scan mode in APCI under positive ionization mode. Analytes were identified by exact mass, correspondence of isotopic cluster and retention times. The limits of detection obtained varied from 10 to 50 pg mg{sup −1}, and limits of quantitation were 0.5 ng mg{sup −1} for all compounds. The method was linear for all analytes in the ranges from the LOQ to 6 ng mg{sup −1}, giving correlation coefficients >0.99 for all analytes. Also accuracy (intended as %E) and repeatability (%CV) were always lower than 15%. Specificity was assessed by analysing ten blank samples and fifteen samples from polidrug abusers. This method was applied to a real-life case, resulting in the identification of testosterone undecanoate in the hair of a suspect. The analyte identity was confirmed by the analysis of its in-source fragmentation and comparison to a certified standard. Thanks to the scan acquisition, this method also enables retrospective re-analysis of the acquired datafile in case a further analyte needs to be screened.

  17. Determination of stimulants using gas chromatography/high-resolution time-of-flight mass spectrometry and a soft ionization source.

    Science.gov (United States)

    Lopez-Avila, Viorica; Cooley, James; Urdahl, Randall; Thevis, Mario

    2012-12-15

    The aim of this study was to investigate the mass spectral fragmentation of a small set of stimulants in a high-resolution time-of-flight mass spectrometer equipped with a soft ionization source using vacuum ultraviolet (VUV) photons emitted from different plasma gases. It was postulated that the use of a plasma gas such as Xe, which emits photons at a lower energy than Kr or Ar, would lead to softer ionization of the test compounds, and thus to less fragmentation. A set of nine stimulants: cocaine, codeine, nicotine, methadone, phenmetrazine, pentylenetetrazole, niketamide, fencamfamine, and caffeine, was analyzed by gas chromatography/time-of-flight mass spectrometry (GC/TOFMS) in positive ion mode with this soft ionization source, using either Xe, Kr, or Ar as plasma gases. Working solutions of the test compounds at 0.1 to 100 ng/μL were used to establish instrument sensitivity and linearity. All test compounds, except methadone and pentylenetetrazole, exhibited strong molecular ions and no fragmentation with Xe-microplasma photoionization (MPPI). Methadone exhibited significant fragmentation not only with Xe, but also with Kr and Ar, and pentylenetetrazole could not be ionized with Xe, probably because its ionization energy is above 8.44 eV. The Kr- and Ar-MPPI mass spectra of the test compounds showed that the relative intensity of the molecular ion decreased as the photon energy increased. When coupled to a TOF mass spectrometer this soft ionization source has demonstrated signal-to-noise (S/N) ratios from 7 to 730 at 100 pg per injection (depending on the compound), and a dynamic range of three orders of magnitude (100 pg to 100 ng) for some of the test compounds. Copyright © 2012 John Wiley & Sons, Ltd.

  18. A hybrid approach to urine drug testing using high-resolution mass spectrometry and select immunoassays.

    Science.gov (United States)

    McMillin, Gwendolyn A; Marin, Stephanie J; Johnson-Davis, Kamisha L; Lawlor, Bryan G; Strathmann, Frederick G

    2015-02-01

    The major objective of this research was to propose a simplified approach for the evaluation of medication adherence in chronic pain management patients, using liquid chromatography time-of-flight (TOF) mass spectrometry, performed in parallel with select homogeneous enzyme immunoassays (HEIAs). We called it a "hybrid" approach to urine drug testing. The hybrid approach was defined based on anticipated positivity rates, availability of commercial reagents for HEIAs, and assay performance, particularly analytical sensitivity and specificity for drug(s) of interest. Subsequent to implementation of the hybrid approach, time to result was compared with that observed with other urine drug testing approaches. Opioids, benzodiazepines, zolpidem, amphetamine-like stimulants, and methylphenidate metabolite were detected by TOF mass spectrometry to maximize specificity and sensitivity of these 37 drug analytes. Barbiturates, cannabinoid metabolite, carisoprodol, cocaine metabolite, ethyl glucuronide, methadone, phencyclidine, propoxyphene, and tramadol were detected by HEIAs that performed adequately and/or for which positivity rates were very low. Time to result was significantly reduced compared with the traditional approach. The hybrid approach to urine drug testing provides a simplified and analytically specific testing process that minimizes the need for secondary confirmation. Copyright© by the American Society for Clinical Pathology.

  19. Photolysis of Antibiotics under Simulated Sunlight Irradiation: Identification of Photoproducts by High-Resolution Mass Spectrometry.

    Science.gov (United States)

    Baena-Nogueras, Rosa María; González-Mazo, Eduardo; Lara-Martín, Pablo A

    2017-02-28

    There is growing concern regarding the widespread use of antibiotics and their presence in the aqueous environment. Their removal in the water column is mediated by different types of degradation processes for which the mechanisms are still unclear. This research is focused on characterizing the photodegradation kinetics and pathways of two largely employed antibiotics families: sulfonamides (9 SDs) and fluoroquinolones (6 FQs). Degradation percentages and rates were measured in pure water exposed to simulated natural sunlight at a constant irradiance value (500 W m(-2)) during all the experiments, and the main photoproducts formed were characterized through accurate mass measurement using ultraperformance liquid chromatography-quadrupole-time-of-flight-mass spectrometry (UPLC-QToF-MS). Over 200 different phototransformation products were identified for SDs and FQs, 66% of them, to the best of our knowledge, have not been described before. Their sequential formation and disappearance over the course of the experiments reveals the existence of several pathways for the degradation of target antibiotics. Occurrence of new photoproducts derived from desulfonation and/or denitrification, as well as hydroxylation of photo-oxidized heterocyclic rings, have been identified during photodegradation of SDs, whereas a new pathway yielding oxidation of the benzene ring after the cleavage of the piperazine ring (e.g., CIP product with m/z 280) is described for FQs.

  20. Decon2LS: An open-source software package for automated processing and visualization of high resolution mass spectrometry data

    Directory of Open Access Journals (Sweden)

    Anderson Gordon A

    2009-03-01

    Full Text Available Abstract Background Data generated from liquid chromatography coupled to high-resolution mass spectrometry (LC-MS-based studies of a biological sample can contain large amounts of biologically significant information in the form of proteins, peptides, and metabolites. Interpreting this data involves inferring the masses and abundances of biomolecules injected into the instrument. Because of the inherent complexity of mass spectral patterns produced by these biomolecules, the analysis is significantly enhanced by using visualization capabilities to inspect and confirm results. In this paper we describe Decon2LS, an open-source software package for automated processing and visualization of high-resolution MS data. Drawing extensively on algorithms developed over the last ten years for ICR2LS, Decon2LS packages the algorithms as a rich set of modular, reusable processing classes for performing diverse functions such as reading raw data, routine peak finding, theoretical isotope distribution modelling, and deisotoping. Because the source code is openly available, these functionalities can now be used to build derivative applications in relatively fast manner. In addition, Decon2LS provides an extensive set of visualization tools, such as high performance chart controls. Results With a variety of options that include peak processing, deisotoping, isotope composition, etc, Decon2LS supports processing of multiple raw data formats. Deisotoping can be performed on an individual scan, an individual dataset, or on multiple datasets using batch processing. Other processing options include creating a two dimensional view of mass and liquid chromatography (LC elution time features, generating spectrum files for tandem MS data, creating total intensity chromatograms, and visualizing theoretical peptide profiles. Application of Decon2LS to deisotope different datasets obtained across different instruments yielded a high number of features that can be used to

  1. United States Strategy Toward China After a Peaceful Taiwan Strait Resolution

    Science.gov (United States)

    2005-12-01

    Furthermore, former Singapore Prime Minister Lee Kuan Yew has predicted East Asia will move towards an economic system where China will become the leading...Christoffersen, “The Role of East Asia in Sino-American Relations,” Asian Survey 42, no. 3 (2002): 374. 128 Lee Kuan Yew , interview by Hans Hoyng and...respects, China is emulating the path pursued by the United States in the post-World War II era—leveraging economic 187 Lee Kuan Yew , “Competition in

  2. Clustering, methodology, and mechanistic insights into acetate chemical ionization using high-resolution time-of-flight mass spectrometry

    Science.gov (United States)

    Brophy, Patrick; Farmer, Delphine K.

    2016-08-01

    We present a comprehensive characterization of cluster control and transmission through the Tofwerk atmospheric pressure interface installed on various chemical ionization time-of-flight mass spectrometers using authentic standards. This characterization of the atmospheric pressure interface allows for a detailed investigation of the acetate chemical ionization mechanisms and the impact of controlling these mechanisms on sensitivity, selectivity, and mass spectral ambiguity with the aim of non-targeted analysis. Chemical ionization with acetate reagent ions is controlled by a distribution of reagent ion-neutral clusters that vary with relative humidity and the concentration of the acetic anhydride precursor. Deprotonated carboxylic acids are primarily detected only if sufficient declustering is employed inside the atmospheric pressure interface. The configuration of a high-resolution time-of-flight chemical ionization mass spectrometer (HR-TOF-CIMS) using an acetate chemical ionization source for non-targeted analysis is discussed. Recent approaches and studies characterizing acetate chemical ionization as it applies to the HR-TOF-CIMS are evaluated in light of the work presented herein.

  3. Novel approaches in analysis of Fusarium mycotoxins in cereals employing ultra performance liquid chromatography coupled with high resolution mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Zachariasova, M.; Lacina, O.; Malachova, A.; Kostelanska, M.; Poustka, J. [Institute of Chemical Technology, Faculty of Food and Biochemical Technology, Department of Food Chemistry and Analysis, Technicka 3, 166 28 Prague 6 (Czech Republic); Godula, M. [Thermo Fisher Scientific, Czech Republic, Slunecna 27, 100 00 Prague 10 (Czech Republic); Hajslova, J., E-mail: jana.hajslova@vscht.cz [Institute of Chemical Technology, Faculty of Food and Biochemical Technology, Department of Food Chemistry and Analysis, Technicka 3, 166 28 Prague 6 (Czech Republic)

    2010-03-03

    Rapid, simple and cost-effective analytical methods with performance characteristics matching regulatory requirements are needed for effective control of occurrence of Fusarium toxins in cereals and cereal-based products to which they might be transferred during processing. Within this study, two alternative approaches enabling retrospective data analysis and identification of unknown signals in sample extracts have been implemented and validated for determination of 11 major Fusarium toxins. In both cases, ultra-high performance liquid chromatography (U-HPLC) coupled with high resolution mass spectrometry (HR MS) was employed. {sup 13}C isotopically labeled surrogates as well as matrix-matched standards were employed for quantification. As far as time of flight mass analyzer (TOF-MS) was a detection tool, the use of modified QuEChERS (quick easy cheap effective rugged and safe) sample preparation procedure, widely employed in multi-pesticides residue analysis, was shown as an optimal approach to obtain low detection limits. The second challenging alternative, enabling direct analysis of crude extract, was the use of mass analyzer based on Orbitrap technology. In addition to demonstration of full compliance of the new methods with Commission Regulation (EC) No. 401/2006, also their potential to be used for confirmatory purposes according to Commission Decision 2002/657/EC has been critically assessed.

  4. Molecular characterization of monoterpene ozonolysis products using ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry

    Science.gov (United States)

    Kundu, S.; Fisseha, R.; Putman, A.; Rahn, T.; Mazzoleni, L. R.

    2010-12-01

    A detailed knowledge of the chemical composition of secondary organic aerosols (SOA) is required to better understand their roles in climate change, biogeochemical cycling and public health. The chemical composition of the SOA produced by the ozonolysis of limonene was investigated using electrospray ionization Fourier transform ion cyclotron resonance (ESI FT-ICR) mass spectrometry. SOA was generated in a 1.5 m3 teflon chamber with 500 ppb of limonene and 250 ppb of O3, without the presence of hydroxyl radical scavenger. We have identified approximately 1300-1500 molecular masses from negative-ion spectra in the range of 105 Putman et al., 2010). We will compare the chemical composition of limonene-SOA with that of α- and β-pinene-SOA. We will also discuss the MSn fragmentation behavior of major ions for the structural elucidation of the oligomers. Putman, A., J. Offenberg, R. Fisseha, T. Rahn, and L. R. Mazzoleni, Ultrahigh-resolution mass spectrometry of the complex secondary organic aerosol products from ozonolysis of α-pinene: Investigating oligomers, in preparation, 2010.

  5. Simultaneous determination of 40 novel psychoactive stimulants in urine by liquid chromatography-high resolution mass spectrometry and library matching.

    Science.gov (United States)

    Concheiro, Marta; Castaneto, Marisol; Kronstrand, Robert; Huestis, Marilyn A

    2015-06-05

    The emergence of novel psychoactive substances is an ongoing challenge for analytical toxicologists. Different analogs are continuously introduced in the market to circumvent legislation and to enhance their pharmacological activity. Although detection of drugs in blood indicates recent exposure and link intoxication to the causative agent, urine is still the most preferred testing matrix in clinical and forensic settings. We developed a method for the simultaneous quantification of 8 piperazines, 4 designer amphetamines and 28 synthetic cathinones and 4 metabolites, in urine by liquid chromatography coupled to high-resolution mass spectrometry (LC-HRMS). Data were acquired in full scan and data dependent MS(2) mode. Compounds were quantified by precursor ion exact mass, and confirmed by product ion spectra library matching, taking into account product ions' exact mass and intensities. One-hundred μL urine was subjected to solid phase cation exchange extraction (SOLA SCX). The chromatographic reverse-phase separation was achieved with gradient mobile phase of 0.1% formic acid in water and in acetonitrile in 20 min. The assay was linear from 2.5 or 5 to 500 μg/L. Imprecision (n=15) was urine specimens (n=62) were analyzed with the method that provides a comprehensive confirmation for 40 new stimulant drugs with specificity and sensitivity.

  6. Rapid in situ identification of bioactive compounds in plants by in vivo nanospray high-resolution mass spectrometry.

    Science.gov (United States)

    Chang, Qing; Peng, Yue'e; Dan, Conghui; Shuai, Qin; Hu, Shenghong

    2015-03-25

    A method for the rapid in situ identification of bioactive compounds in fresh plants has been developed using in vivo nanospray coupled to high-resolution mass spectrometry (HR-MS). Using a homemade in vivo nanospray ion source, the plant liquid was drawn out from a target region and ionized in situ. The ionized bioactive compounds were then identified using Q-Orbitrap HR-MS. The accurate mass measurements of these bioactive compounds were performed by full-scan or selected ion monitoring (SIM), and tandem mass spectrometry (MS/MS) was used in the structural elucidation. Without sample pretreatment, 12 bioactive compounds in 7 different plant species were identified, namely, isoalliin in onion; butylphthalide in celery; N-methylpelletierine, pelletierine, and pseudopelletierine in pomegranate; chlorogenic acid in crabapple; solamargine, solasonine, and solasodine in nightshade; aloin and aloe-emodin in aloe; and menthone in mint. This work demonstrates that in vivo nanospray HR-MS is a good method for rapid in situ identification of bioactive compounds in plants.

  7. Analysis of the Fusarium mycotoxin moniliformin in cereal samples using 13C2-moniliformin and high-resolution mass spectrometry.

    Science.gov (United States)

    von Bargen, Katharina Walburga; Lohrey, Lilia; Cramer, Benedikt; Humpf, Hans-Ulrich

    2012-04-11

    Moniliformin is a mycotoxin produced by fungi of the Fusarium genus and occurs as a contaminant of different cereals worldwide. This study describes the first application of isotopically labeled (13)C(2)-moniliformin for the analysis of moniliformin in cereals. Moniliformin is a small and ionic molecule that forms only a single sensitive fragment ion in the collision cell of a tandem mass spectrometer. Therefore, the methods described in the literature for this kind of instrument observe only a single mass transition and show a relatively poor sensitivity. The use of high-resolution mass spectrometry was described to be a suitable alternative technique for the detection of this compound and was therefore applied in this study. The developed method is based on the use of strong anion exchange columns for cleanup prior to HPLC analysis and has a recovery rate of 75.3%, a limit of detection (LOD) of 0.7 μg/kg, and a limit of quantitation (LOQ) of 2.5 μg/kg. Twenty-three different cereal samples were analyzed for their moniliformin content. Twenty of them showed positive results with levels up to 126 ± 12.2 μg/kg.

  8. Measurement of the Black Hole Mass in NGC 1332 from ALMA Observations at 0.044 Arcsecond Resolution

    CERN Document Server

    Barth, Aaron J; Darling, Jeremy; Baker, Andrew J; Buote, David A; Ho, Luis C; Walsh, Jonelle L

    2016-01-01

    We present Atacama Large Millimeter/submillimeter Array (ALMA) Cycle 3 observations of CO(2-1) emission from the circumnuclear disk in the E/S0 galaxy NGC 1332 at 0.044" resolution. The disk exhibits regular rotational kinematics and central high-velocity emission (+/-500 km/s) consistent with the presence of a compact central mass. We construct models for a thin, dynamically cold disk in the gravitational potential of the host galaxy and black hole, and fit the beam-smeared model line profiles directly to the ALMA data cube. Model fits successfully reproduce the disk kinematics out to r=200 pc. Fitting models just to spatial pixels within projected r=50 pc of the nucleus (two times larger than the black hole's gravitational radius of influence), we find M_BH=6.64(-0.63,+0.65)*10^8 solar masses. This observation demonstrates ALMA's powerful capability to determine the masses of supermassive black holes by resolving gas kinematics on small angular scales in galaxy nuclei.

  9. Subarcsecond resolution observations of warm water towards three deeply embedded low-mass protostars

    DEFF Research Database (Denmark)

    Persson, Magnus Vilhelm; Jørgensen, Jes Kristian; van Dishoeck, Ewine F.

    2012-01-01

    Water is present during all stages of star formation: as ice in the cold outer parts of protostellar envelopes and dense inner regions of circumstellar disks, and as gas in the envelopes close to the protostars, in the upper layers of circumstellar disks and in regions of powerful outflows...... and shocks. In this paper we probe the mechanism regulating the warm gas-phase water abundance in the innermost hundred AU of deeply embedded (Class~0) low-mass protostars, and investigate its chemical relationship to other molecular species during these stages. Millimeter wavelength thermal emission from...... in the IRAS4A binary; in addition CH3OCH3, C2H5CN, and SO2 are detected. Extended water emission is seen towards IRAS2A, possibly associated with the outflow. The detections in all systems suggests that the presence of water on 96 %) is frozen out on dust grains at these scales. The derived abundances of CH3...

  10. Assessing PM2.5 Exposures with High Spatiotemporal Resolution across the Continental United States.

    Science.gov (United States)

    Di, Qian; Kloog, Itai; Koutrakis, Petros; Lyapustin, Alexei; Wang, Yujie; Schwartz, Joel

    2016-05-01

    A number of models have been developed to estimate PM2.5 exposure, including satellite-based aerosol optical depth (AOD) models, land-use regression, or chemical transport model simulation, all with both strengths and weaknesses. Variables like normalized difference vegetation index (NDVI), surface reflectance, absorbing aerosol index, and meteoroidal fields are also informative about PM2.5 concentrations. Our objective is to establish a hybrid model which incorporates multiple approaches and input variables to improve model performance. To account for complex atmospheric mechanisms, we used a neural network for its capacity to model nonlinearity and interactions. We used convolutional layers, which aggregate neighboring information, into a neural network to account for spatial and temporal autocorrelation. We trained the neural network for the continental United States from 2000 to 2012 and tested it with left out monitors. Ten-fold cross-validation revealed a good model performance with a total R(2) of 0.84 on the left out monitors. Regional R(2) could be even higher for the Eastern and Central United States. Model performance was still good at low PM2.5 concentrations. Then, we used the trained neural network to make daily predictions of PM2.5 at 1 km × 1 km grid cells. This model allows epidemiologists to access PM2.5 exposure in both the short-term and the long-term.

  11. Preventing cervical cancer in the United States: barriers and resolutions for HPV vaccination

    Directory of Open Access Journals (Sweden)

    Anna Louise Beavis

    2016-02-01

    Full Text Available HPV vaccination rates for preadolescent and adolescent girls in the United States are far behind those of other developed nations. These rates differ substantially by region and state, socioeconomic status, and insurance status. In parents and young women, a lack of awareness and a misperception of the risk of this vaccine drive low vaccination rates. In physicians, lack of comfort with discussion of sexuality, and the perception that the vaccine should be delayed to a later age contribute to low vaccination rates. Patient and physician-targeted educational campaigns, systems-based interventions, and school-based vaccine clinics offer a variety of ways to address the barriers to HPV vaccination. A diverse and culturally appropriate approach to promoting vaccine uptake has the potential to significantly improve vaccination rates in order to reach the Healthy People 2020 goal of over 80% vaccination in adolescent girls. This article reviews the disparities in HPV vaccination rates in girls in the United States, the influences of patients’, physicians’ and parents’ attitudes on vaccine uptake, and the proposed interventions that may help the US reach its goal for vaccine coverage.

  12. Analyzing high resolution topography for advancing the understanding of mass and energy transfer through landscapes: A review

    Science.gov (United States)

    Passaiacquaa, Paola; Belmont, Patrick; Staley, Dennis M.; Simley, Jeffery; Arrowsmith, J. Ramon; Bode, Collin A.; Crosby, Christopher; DeLong, Stephen; Glenn, Nancy; Kelly, Sara; Lague, Dimitri; Sangireddy, Harish; Schaffrath, Keelin; Tarboton, David; Wasklewicz, Thad; Wheaton, Joseph

    2015-01-01

    The study of mass and energy transfer across landscapes has recently evolved to comprehensive considerations acknowledging the role of biota and humans as geomorphic agents, as well as the importance of small-scale landscape features. A contributing and supporting factor to this evolution is the emergence over the last two decades of technologies able to acquire high resolution topography (HRT) (meter and sub-meter resolution) data. Landscape features can now be captured at an appropriately fine spatial resolution at which surface processes operate; this has revolutionized the way we study Earth-surface processes. The wealth of information contained in HRT also presents considerable challenges. For example, selection of the most appropriate type of HRT data for a given application is not trivial. No definitive approach exists for identifying and filtering erroneous or unwanted data, yet inappropriate filtering can create artifacts or eliminate/distort critical features. Estimates of errors and uncertainty are often poorly defined and typically fail to represent the spatial heterogeneity of the dataset, which may introduce bias or error for many analyses. For ease of use, gridded products are typically preferred rather than the more information-rich point cloud representations. Thus many users take advantage of only a fraction of the available data, which has furthermore been subjected to a series of operations often not known or investigated by the user. Lastly, standard HRT analysis work-flows are yet to be established for many popular HRT operations, which has contributed to the limited use of point cloud data.In this review, we identify key research questions relevant to the Earth-surface processes community within the theme of mass and energy transfer across landscapes and offer guidance on how to identify the most appropriate topographic data type for the analysis of interest. We describe the operations commonly performed from raw data to raster products and

  13. High-resolution Continental Scale Land Surface Model incorporating Land-water Management in United States

    Science.gov (United States)

    Shin, S.; Pokhrel, Y. N.

    2016-12-01

    Land surface models have been used to assess water resources sustainability under changing Earth environment and increasing human water needs. Overwhelming observational records indicate that human activities have ubiquitous and pertinent effects on the hydrologic cycle; however, they have been crudely represented in large scale land surface models. In this study, we enhance an integrated continental-scale land hydrology model named Leaf-Hydro-Flood to better represent land-water management. The model is implemented at high resolution (5km grids) over the continental US. Surface water and groundwater are withdrawn based on actual practices. Newly added irrigation, water diversion, and dam operation schemes allow better simulations of stream flows, evapotranspiration, and infiltration. Results of various hydrologic fluxes and stores from two sets of simulation (one with and the other without human activities) are compared over a range of river basin and aquifer scales. The improved simulations of land hydrology have potential to build consistent modeling framework for human-water-climate interactions.

  14. Analysis of the chemical composition of organic aerosol at the Mt. Sonnblick observatory using a novel high mass resolution thermal-desorption proton-transfer-reaction mass-spectrometer (hr-TD-PTR-MS)

    NARCIS (Netherlands)

    Holzinger, R.|info:eu-repo/dai/nl/337989338; Kasper-Giebl, A.; Staudinger, M.; Schauer, G.; Roeckmann, T.|info:eu-repo/dai/nl/304838233

    2010-01-01

    For the first time a high mass resolution thermal desorption proton transfer reaction mass spectrometer (hr-TD-PTR-MS) was deployed in the field to analyze the composition of the organic fraction of aerosols. We report on measurements from the remote Mt. Sonnblick observatory in the Austrian alps

  15. Simulating Land Surface Hydrology at a 30-meter Spatial Resolution over the Contiguous United States

    Science.gov (United States)

    Wood, E. F.; Pan, M.; Cai, X.; Chaney, N.

    2016-12-01

    Big data, high performance computing, and recent advances in hydrologic similarity present a unique opportunity for macroscale hydrology: the land surface hydrology can be modeled at field scales over continental extents while ensuring computational efficiency to enable robust ensemble frameworks. In this presentation we will illustrate this potential breakthrough in macroscale hydrology by discussing results from a 30-meter simulation over the contiguous United States using the HydroBlocks land surface model. HydroBlocks is a novel land surface model that represents field-scale spatial heterogeneity of land surface processes through interacting hydrologic response units (HRUs) [Chaney et al., 2016]. The model is a coupling between the Noah-MP land surface model and the Dynamic TOPMODEL hydrologic model. The HRUs are defined by clustering proxies of the drivers of spatial heterogeneity using hyperresolution land data. For the simulations over CONUS, HydroBlocks is run at every HUC10 catchment using 100 HRUs per catchment between 2004 and 2014. The simulations are forced with the 4 km Stage IV radar rainfall product and a spatially downscaled version of NLDAS-2. We will show how this approach to macroscale hydrology ensures computational efficiency while providing field-scale hydrologic information over continental extents. We will illustrate how this approach provides a novel approach in both the application and validation of macroscale land surface and hydrologic models. Finally, using these results, we will discuss the important role that big data and high performance computing can play in providing solutions to longstanding challenges to not only flood and drought monitoring systems but also to numerical weather prediction, seasonal forecasting, and climate prediction. References Chaney, N., P. Metcalfe, and E. F. Wood (2016), HydroBlocks: A Field-scale Resolving Land Surface Model for Application Over Continental Extents, Hydrological Processes, (in press.)

  16. Analytical strategy to investigate 3,4-methylenedioxypyrovalerone (MDPV) metabolites in consumers' urine by high-resolution mass spectrometry.

    Science.gov (United States)

    Ibáñez, María; Pozo, Óscar J; Sancho, Juan V; Orengo, Teresa; Haro, Gonzalo; Hernández, Félix

    2016-01-01

    The potential of high-resolution mass spectrometry (HRMS) for the investigation of human in vivo metabolism of 3,4-methylenedioxypyrovalerone (MDPV) using urine collected from a consumer (this is, in non-controlled experiments) has been investigated. As a control sample was not available, the common approach based on the comparison of a control/blank sample and samples collected after drug intake could not be used. Alternatively, an investigation based on common fragmentation pathways was applied, assuming that most metabolites share some fragments with the parent drug. An extension of this approach was also applied based on the fragmentation pathway of those metabolites identified in urine samples in the first step. The use of MS(E) experiments (sequential acquisition of mass spectra at low and high collision energy) has been crucial to this aim as it allowed promoting fragmentation in the collision cell without any previous precursor ion selection. MDPV belongs to the group of new psychoactive substances (NPS), being known as the "cannibal drug". This substance is being abused more and more and is associated with dangerous side effects. The human metabolites (both phase I and phase II) were detected and tentatively identified by accurate mass full-spectrum measurements using ultra-high performance liquid chromatography coupled to hybrid quadrupole time-of-flight mass spectrometry (UHPLC-QTOF MS). Following this strategy, up to 10 phase I metabolites, together with some glucuronides and sulphates, were detected and tentative structures were proposed. Several compounds identified in this work have not been previously reported in the literature.

  17. High-Resolution Mass Spectrometry and Molecular Characterization of Aqueous Photochemistry Products of Common Types of Secondary Organic Aerosols

    Energy Technology Data Exchange (ETDEWEB)

    Romonosky, Dian E.; Laskin, Alexander; Laskin, Julia; Nizkorodov, Sergey

    2015-03-19

    A significant fraction of atmospheric organic compounds is predominantly found in condensed phases, such as aerosol particles and cloud droplets. Many of these compounds are photolabile and can degrade through direct photolysis or indirect photooxidation processes on time scales that are comparable to the typical lifetimes of aqueous droplets (hours) and particles (days). This paper presents a systematic investigation of the molecular level composition and the extent of aqueous photochemical processing in different types of secondary organic aerosol (SOA) from biogenic and anthropogenic precursors including α-pinene, β-pinene, β-myrcene, d- limonene, α-humulene, 1,3,5-trimethylbenzene, and guaiacol, oxidized by ozone (to simulate a remote atmosphere) or by OH in the presence of NOx (to simulate an urban atmosphere). Chamber- and flow tube-generated SOA samples were collected, extracted in a methanol/water solution, and photolyzed for 1 h under identical irradiation conditions. In these experiments, the irradiation was equivalent to about 3-8 h of exposure to the sun in its zenith. The molecular level composition of the dissolved SOA was probed before and after photolysis with direct-infusion electrospray ionization high-resolution mass spectrometry (ESI-HR-MS). The mass spectra of unphotolyzed SOA generated by ozone oxidation of monoterpenes showed qualitatively similar features, and contained largely overlapping subsets of identified compounds. The mass spectra of OH/NOx generated SOA had more unique visual appearance, and indicated a lower extent of products overlap. Furthermore, the fraction of nitrogen containing species (organonitrates and nitroaromatics) was highly sensitive to the SOA precursor. These observations suggest that attribution of high-resolution mass spectra in field SOA samples to specific SOA precursors should be more straightforward under OH/NOx oxidation conditions compared to the ozone driven oxidation. Comparison of the SOA constituents

  18. Exploring the Behaviour of Emerging Contaminants in the Water Cycle using the Capabilities of High Resolution Mass Spectrometry.

    Science.gov (United States)

    Hollender, Juliane; Bourgin, Marc; Fenner, Kathrin B; Longrée, Philipp; Mcardell, Christa S; Moschet, Christoph; Ruff, Matthias; Schymanski, Emma L; Singer, Heinz P

    2014-11-01

    To characterize a broad range of organic contaminants and their transformation products (TPs) as well as their loads, input pathways and fate in the water cycle, the Department of Environmental Chemistry (Uchem) at Eawag applies and develops high-performance liquid chromatography (LC) methods combined with high-resolution tandem mass spectrometry (HRMS/MS). In this article, the background and state-of-the-art of LC-HRMS/MS for detection of i) known targets, ii) suspected compounds like TPs, and iii) unknown emerging compounds are introduced briefly. Examples for each approach are taken from recent research projects conducted within the department. These include the detection of trace organic contaminants and their TPs in wastewater, pesticides and their TPs in surface water, identification of new TPs in laboratory degradation studies and ozonation experiments and finally the screening for unknown compounds in the catchment of the river Rhine.

  19. Study of the mass and energy resolution of the E parallel B charge exchange analyzer for TFTR

    Energy Technology Data Exchange (ETDEWEB)

    Kaita, R.; Medley, S.S.

    1979-09-01

    The charge exchange diagnostic for TFTR requires simultaneous multispecie (H/sup +/, D/sup +/, ..gamma../sup +/) analysis of particles in the energy range of 0.5 - 150 keV. The analyzer design chosen to provide this capability employs a wide gap semi-circular region of superimposed parallel electric and magnetic fields to accomplish mass and energy resolution, respectively. Combined with a large area, multi-anode microchannel plate detector, this arrangement will enable the energy distributions of protons, deuterions, and tritons to be measured concurrently as a function of time during each discharge. A computer simulation program for calculating ion trajectories through the analyzer was written that includes a realistic model of the magnetic and electrostatic fringe fields. This report presents the results of a study of the proposed E parallel B analyzer, and it reveals that the fringe fields are not detrimental to the performance of the analyzer.

  20. Elemental Composition Analysis to Investigate NOx Effects on Secondary Organic Aerosol from α-Pinene Using Ultrahigh Resolution Mass Spectrometry

    Science.gov (United States)

    Lim, H. J.; Park, J. H.; Babar, Z.

    2015-12-01

    Secondary organic aerosol (SOA) accounts for 20-70% of atmospheric fine aerosol. NOx plays crucial roles in SOA formation and consequently affects the composition and yield of SOA. SOA component speciation is incomplete due to its complex composition of polar oxygenated and multifunctional species. In this study, ultrahigh resolution mass spectrometry (UHR MS) was applied to improve the understanding of NOx effects on biogenic SOA formation by identifying the elemental composition of SOA. Additional research aim was to investigate oligomer components that are considered as a driving force for SOA formation and growth. In this study α-pinene SOA from photochemical reaction was examined. SOA formation was performed in the absence and presence of NOx at dry condition (government (MEST) (No. 2011-01350000).

  1. Liquid chromatography-high-resolution mass spectrometry for pesticide residue analysis in fruit and vegetables: screening and quantitative studies.

    Science.gov (United States)

    Gómez-Ramos, M M; Ferrer, C; Malato, O; Agüera, A; Fernández-Alba, A R

    2013-04-26

    This work reviews the current state-of-the-art of liquid chromatography coupled to high-resolution mass spectrometry (LC-HRMS) techniques applied to the analysis of pesticides in fruit-based and vegetable-based matrices. Nowadays, simultaneous trace analysis of hundreds of pesticides from different classes is required, preferably in just one run. The most commonly used QqQ-MS technology presents certain limitations in its application in a cost and effective way when analyzing a large number of pesticides. Thus, this review includes HRMS technology as a reliable complementary alternative allowing the analysis of a wide range of pesticides in food. Its capabilities and limitations in identifying, confirming and quantifying pesticides are discussed. HRMS instruments can adequately address such issues; however, the main drawbacks are as a result of insufficient prior optimization of the operational parameters during non-target analysis in full-scan mode and due to software shortcomings.

  2. Gas-phase fragmentation of peptides to increase the spatial resolution of the Hydrogen Exchange Mass Spectrometry experiment

    DEFF Research Database (Denmark)

    Jensen, Pernille Foged; Rand, Kasper Dyrberg

    2016-01-01

    Generation of overlapping peptides in solution via multiple proteases requires a very high peak capacity for the LC-MS analysis to minimize signal overlap. An inherent advantage of a gas-phase fragmentation step is that the additional gas-phase fragment ions used to sublocalize deuterium...... are produced after precursor ion selection and thus do not add complexity to the LC-MS analysis. The key to obtaining optimal spatial resolution in a hydrogen exchange mass spectrometry (HX-MS) experiment is the fragmentation efficiency. This chapter discusses common fragmentation techniques like collision......-induced dissociation (CID) occur with complete Hydrogen-deuterium (H/D) scrambling, while other techniques that induce dissociation on a faster timescale through radical-based fragmentation channels, like electron-capture dissociation (ECD) and electron-transfer dissociation (ETD), occur inherently without H...

  3. Characterization of Rainwater Dissolved Organic Matter by Ultrahigh Resolution Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

    Science.gov (United States)

    Mead, R. N.; Podgorski, D. C.; Mullaugh, K. M.; Avery, B.; Kieber, R. J.; Willey, J. D.; Cooper, W. T.

    2011-12-01

    Rainwater is a complex, heterogeneous mixture of dissolved organic matter (DOM) that remains largely uncharacterized at the molecular level. Rainwater with dissolved organic carbon values ranging from 3 to 450 μM was collected during 40 separate rain events from 2007-2011 that included coastal and terrestrial storms based upon 36 hour back trajectories. Individual rain samples were lypholized and solvent added in preparation for analysis by negative electrospray ionization and atmospheric pressure photoionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). This data set is unique in that each rain event was analyzed individually and not combined allowing for unprecedented insight into rainwater DOM at the molecular level on an episodic basis. Unique elemental compositions were assigned for compounds belonging to CHO, CHOS and CHON classes. Data visualization by van Krevelen diagrams showed clear differences in coastal and terrestrial storm events with a majority of coastal storms having high H/C (1.5-2.0) relative to terrestrial storms. Further inspection of the data revealed that rainwater has relatively high O/C (1.4) and low H/C (<0.5) which suggests rainwater DOM is compositionally different than fog water, water soluble organic carbon isolated from aerosols and surface waters.

  4. Nontargeted modification-specific metabolomics study based on liquid chromatography-high-resolution mass spectrometry.

    Science.gov (United States)

    Dai, Weidong; Yin, Peiyuan; Zeng, Zhongda; Kong, Hongwei; Tong, Hongwei; Xu, Zhiliang; Lu, Xin; Lehmann, Rainer; Xu, Guowang

    2014-09-16

    Modifications of genes and proteins have been extensively studied in systems biology using comprehensive analytical strategies. Although metabolites are frequently modified, these modifications have not been studied using -omics approaches. Here a general strategy for the nontargeted profiling of modified metabolites, which we call "nontargeted modification-specific metabolomics", is reported. A key aspect of this strategy was the combination of in-source collision-induced dissociation liquid chromatography-mass spectrometry (LC-MS) and global nontargeted LC-MS-based metabolomics. Characteristic neutral loss fragments that are specific for acetylation, sulfation, glucuronidation, glucosidation, or ribose conjugation were reproducibly detected using human urine as a model specimen for method development. The practical application of this method was demonstrated by profiling urine samples from liver cirrhosis patients. Approximately 900 features were identified as modified endogenous metabolites and xenobiotics. Moreover, this strategy supports the identification of compounds not included in traditional metabolomics databases (HMDB, Metlin, and KEGG), which are currently referred to as "unknowns" in metabolomics projects. Nontargeted modification-specific metabolomics opens a new perspective in systems biology.

  5. Identification of Microorganisms by High Resolution Tandem Mass Spectrometry with Accurate Statistical Significance

    Science.gov (United States)

    Alves, Gelio; Wang, Guanghui; Ogurtsov, Aleksey Y.; Drake, Steven K.; Gucek, Marjan; Suffredini, Anthony F.; Sacks, David B.; Yu, Yi-Kuo

    2016-02-01

    Correct and rapid identification of microorganisms is the key to the success of many important applications in health and safety, including, but not limited to, infection treatment, food safety, and biodefense. With the advance of mass spectrometry (MS) technology, the speed of identification can be greatly improved. However, the increasing number of microbes sequenced is challenging correct microbial identification because of the large number of choices present. To properly disentangle candidate microbes, one needs to go beyond apparent morphology or simple `fingerprinting'; to correctly prioritize the candidate microbes, one needs to have accurate statistical significance in microbial identification. We meet these challenges by using peptidome profiles of microbes to better separate them and by designing an analysis method that yields accurate statistical significance. Here, we present an analysis pipeline that uses tandem MS (MS/MS) spectra for microbial identification or classification. We have demonstrated, using MS/MS data of 81 samples, each composed of a single known microorganism, that the proposed pipeline can correctly identify microorganisms at least at the genus and species levels. We have also shown that the proposed pipeline computes accurate statistical significances, i.e., E-values for identified peptides and unified E-values for identified microorganisms. The proposed analysis pipeline has been implemented in MiCId, a freely available software for Microorganism Classification and Identification. MiCId is available for download at http://www.ncbi.nlm.nih.gov/CBBresearch/Yu/downloads.html.

  6. Determination of plastic additives in packaging by liquid chromatography coupled to high resolution mass spectrometry.

    Science.gov (United States)

    Moreta, Cristina; Tena, María-Teresa

    2015-10-02

    A simple and sensitive analytical method for the determination of several plastic additives in multilayer packaging based on solid-liquid extraction (SLE) and ultra-high performance liquid chromatography (UHPLC) coupled to variable wavelength (VWD) and time of flight mass spectrometry (TOF-MS) detectors is presented. The proposed method allows the simultaneous determination of fourteen additives belonging to different families such as antioxidants, slip agents and light stabilizers, as well as two oxidation products in only 9min. The developed method was validated in terms of linearity, matrix effect error, detection and quantification limits, repeatability and intermediate precision. The instrumental method showed satisfactory repeatability and intermediate precision at concentrations closed to LOQ with RSDs less than 7 and 20%, respectively, and LODs until 5000 times more sensitive than other GC-FID and HPLC-VWD methods previously reported. Also, focused ultrasound solid-liquid extraction (FUSLE) was optimized and evaluated to extract plastic additives from packaging. Extraction results obtained by FUSLE and SLE were compared to those obtained by pressurized liquid extraction (PLE). All extraction methods showed excellent extraction efficiency for slip agents, however quantitative recovery of all analytes was achieved only by SLE with just 5ml of hexane for 10h. Finally, the selected method was applied to the analysis of packaging samples where erucamide, Irgafos 168, oxidized Irgafos 168, Irganox 1076 and Irganox 1010 were detected and quantified. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. High spatial resolution mid-infrared observations of the low-mass young star TW Hya

    CERN Document Server

    Ratzka, T; Henning, T; Bouwman, J; Dullemond, C P; Jaffe, W

    2007-01-01

    We want to improve knowledge of the structure of the inner few AU of the circumstellar disk around the nearby T Tauri star TW Hya. Earlier studies have suggested the existence of a large inner hole, possibly caused by interactions with a growing protoplanet. We used interferometric observations in the N-band obtained with the MIDI instrument on the Very Large Telescope Interferometer, together with 10 micron spectra recorded by the infrared satellite Spitzer. The fact that we were able to determine N-band correlated fluxes and visibilities for this comparatively faint source shows that MIR interferometry can be applied to a large number of low-mass young stellar objects. The MIR spectra obtained with Spitzer reveal emission lines from HI (6-5), HI (7-6), and [Ne II] and show that over 90% of the dust we see in this wavelength regime is amorphous. According to the correlated flux measured with MIDI, most of the crystalline material is in the inner, unresolved part of the disk, about 1 AU in radius. The visibil...

  8. Fine resolution mapping of double-strand break sites for human ribosomal DNA units

    Directory of Open Access Journals (Sweden)

    Bernard J. Pope

    2016-12-01

    Full Text Available DNA breakage arises during a variety of biological processes, including transcription, replication and genome rearrangements. In the context of disease, extensive fragmentation of DNA has been described in cancer cells and during early stages of neurodegeneration (Stephens et al., 2011 Stephens et al. (2011 [5]; Blondet et al., 2001 Blondet et al. (2001 [1]. Stults et al. (2009 Stults et al. (2009 [6] reported that human rDNA gene clusters are hotspots for recombination and that rDNA restructuring is among the most common chromosomal alterations in adult solid tumours. As such, analysis of rDNA regions is likely to have significant prognostic and predictive value, clinically. Tchurikov et al. (2015a, 2016 Tchurikov et al. (2015a, 2016 [7,9] have made major advances in this direction, reporting that sites of human genome double-strand breaks (DSBs occur frequently at sites in rDNA that are tightly linked with active transcription - the authors used a RAFT (rapid amplification of forum termini protocol that selects for blunt-ended sites. They reported the relative frequency of these rDNA DSBs within defined co-ordinate ‘windows’ of varying size and made these data (as well as the relevant ‘raw’ sequencing information available to the public (Tchurikov et al., 2015b. Assay designs targeting rDNA DSB hotspots will benefit greatly from the publication of break sites at greater resolution. Here, we re-analyse public RAFT data and make available rDNA DSB co-ordinates to the single-nucleotide level.

  9. Controlling the taxonomic variable: Taxonomic concept resolution for a southeastern United States herbarium portal

    Directory of Open Access Journals (Sweden)

    Nico Franz

    2016-09-01

    Full Text Available Overview. Taxonomic names are imperfect identifiers of specific and sometimes conflicting taxonomic perspectives in aggregated biodiversity data environments. The inherent ambiguities of names can be mitigated using syntactic and semantic conventions developed under the taxonomic concept approach. These include: (1 representation of taxonomic concept labels (TCLs: name sec. source to precisely identify name usages and meanings, (2 use of parent/child relationships to assemble separate taxonomic perspectives, and (3 expert provision of Region Connection Calculus articulations (RCC–5: congruence, [inverse] inclusion, overlap, exclusion that specify how data identified to different-sourced TCLs can be integrated. Application of these conventions greatly increases trust in biodiversity data networks, most of which promote unitary taxonomic 'syntheses' that obscure the actual diversity of expert-held views. Better design solutions allow users to control the taxonomic variable and thereby assess the robustness of their biological inferences under different perspectives. A unique constellation of prior efforts – including the powerful Symbiota collections software platform, the Euler/X multi-taxonomy alignment toolkit, and the "Weakley Flora" which entails 7,000 concepts and more than 75,000 RCC–5 articulations – provides the opportunity to build a first full-scale concept resolution service for SERNEC, the SouthEast Regional Network of Expertise and Collections, currently with 60 member herbaria and 2 million occurrence records. Intellectual merit. We have developed a multi-dimensional, step-wise plan to transition SERNEC's data culture from name- to concept-based practices. (1 We will engage SERNEC experts through annual, regional workshops and follow-up interactions that will foster buy-in and ultimately the completion of 12 community-identified use cases. (2. We will leverage RCC–5 data from the Weakley Flora and further development of

  10. Laser Ablation - Accelerator Mass Spectrometry: An Approach for Rapid Radiocarbon Analyses of Carbonate Archives at High Spatial Resolution.

    Science.gov (United States)

    Welte, Caroline; Wacker, Lukas; Hattendorf, Bodo; Christl, Marcus; Fohlmeister, Jens; Breitenbach, Sebastian F M; Robinson, Laura F; Andrews, Allen H; Freiwald, André; Farmer, Jesse R; Yeman, Christiane; Synal, Hans-Arno; Günther, Detlef

    2016-09-06

    A new instrumental setup, combining laser ablation (LA) with accelerator mass spectrometry (AMS), has been investigated for the online radiocarbon ((14)C) analysis of carbonate records. Samples were placed in an in-house designed LA-cell, and CO2 gas was produced by ablation using a 193 nm ArF excimer laser. The (14)C/(12)C abundance ratio of the gas was then analyzed by gas ion source AMS. This configuration allows flexible and time-resolved acquisition of (14)C profiles in contrast to conventional measurements, where only the bulk composition of discrete samples can be obtained. Three different measurement modes, i.e. discrete layer analysis, survey scans, and precision scans, were investigated and compared using a stalagmite sample and, subsequently, applied to terrestrial and marine carbonates. Depending on the measurement mode, a precision of typically 1-5% combined with a spatial resolution of 100 μm can be obtained. Prominent (14)C features, such as the atomic bomb (14)C peak, can be resolved by scanning several cm of a sample within 1 h. Stalagmite, deep-sea coral, and mollusk shell samples yielded comparable signal intensities, which again were comparable to those of conventional gas measurements. The novel LA-AMS setup allowed rapid scans on a variety of sample materials with high spatial resolution.

  11. High-resolution MALDI mass spectrometry imaging of gallotannins and monoterpene glucosides in the root of Paeonia lactiflora

    Science.gov (United States)

    Li, Bin; Bhandari, Dhaka Ram; Römpp, Andreas; Spengler, Bernhard

    2016-10-01

    High-resolution atmospheric-pressure scanning microprobe matrix-assisted laser desorption/ionization mass spectrometry imaging (AP-SMALDI MSI) at 10 μm pixel size was performed to unravel the spatio-chemical distribution of major secondary metabolites in the root of Paeonia lactiflora. The spatial distributions of two major classes of bioactive components, gallotannins and monoterpene glucosides, were investigated and visualized at the cellular level in tissue sections of P. lactiflora roots. Accordingly, other primary and secondary metabolites were imaged, including amino acids, carbohydrates, lipids and monoterpenes, indicating the capability of untargeted localization of metabolites by using high-resolution MSI platform. The employed AP-SMALDI MSI system provides significant technological advancement in the visualization of individual molecular species at the cellular level. In contrast to previous histochemical studies of tannins using unspecific staining reagents, individual gallotannin species were accurately localized and unequivocally discriminated from other phenolic components in the root tissues. High-quality ion images were obtained, providing significant clues for understanding the biosynthetic pathway of gallotannins and monoterpene glucosides and possibly helping to decipher the role of tannins in xylem cells differentiation and in the defence mechanisms of plants, as well as to investigate the interrelationship between tannins and lignins.

  12. Chemical dereplication of marine actinomycetes by liquid chromatography-high resolution mass spectrometry profiling and statistical analysis.

    Science.gov (United States)

    Forner, David; Berrué, Fabrice; Correa, Hebelin; Duncan, Katherine; Kerr, Russell G

    2013-12-17

    Discovery of novel bioactive metabolites from marine bacteria is becoming increasingly challenging, and the development of novel approaches to improve the efficiency of early steps in the microbial drug discovery process is therefore of interest. For example, current protocols for the taxonomic dereplication of microbial strains generally use molecular tools which do not take into consideration the ability of these selected bacteria to produce secondary metabolites. As the identification of novel chemical entities is one of the key elements driving drug discovery programs, this study reports a novel methodology to dereplicate microbial strains by a metabolomics approach using liquid chromatography-high resolution mass spectrometry (LC-HRMS). In order to process large and complex three dimensional LC-HRMS datasets, the reported method uses a bucketing and presence-absence standardization strategy in addition to statistical analysis tools including principal component analysis (PCA) and cluster analysis. From a closely related group of Streptomyces isolated from geographically varied environments, we demonstrated that grouping bacteria according to the chemical diversity of produced metabolites is reproducible and provides greatly improved resolution for the discrimination of microbial strains compared to current molecular dereplication techniques. Importantly, this method provides the ability to identify putative novel chemical entities as natural product discovery leads. Copyright © 2013 Elsevier B.V. All rights reserved.

  13. Artificial Neural Network for Probabilistic Feature Recognition in Liquid Chromatography Coupled to High-Resolution Mass Spectrometry.

    Science.gov (United States)

    Woldegebriel, Michael; Derks, Eduard

    2017-01-17

    In this work, a novel probabilistic untargeted feature detection algorithm for liquid chromatography coupled to high-resolution mass spectrometry (LC-HRMS) using artificial neural network (ANN) is presented. The feature detection process is approached as a pattern recognition problem, and thus, ANN was utilized as an efficient feature recognition tool. Unlike most existing feature detection algorithms, with this approach, any suspected chromatographic profile (i.e., shape of a peak) can easily be incorporated by training the network, avoiding the need to perform computationally expensive regression methods with specific mathematical models. In addition, with this method, we have shown that the high-resolution raw data can be fully utilized without applying any arbitrary thresholds or data reduction, therefore improving the sensitivity of the method for compound identification purposes. Furthermore, opposed to existing deterministic (binary) approaches, this method rather estimates the probability of a feature being present/absent at a given point of interest, thus giving chance for all data points to be propagated down the data analysis pipeline, weighed with their probability. The algorithm was tested with data sets generated from spiked samples in forensic and food safety context and has shown promising results by detecting features for all compounds in a computationally reasonable time.

  14. A daily, 1 km resolution data set of downscaled Greenland ice sheet surface mass balance (1958-2015)

    Science.gov (United States)

    Noël, Brice; van de Berg, Willem Jan; Machguth, Horst; Lhermitte, Stef; Howat, Ian; Fettweis, Xavier; van den Broeke, Michiel R.

    2016-10-01

    This study presents a data set of daily, 1 km resolution Greenland ice sheet (GrIS) surface mass balance (SMB) covering the period 1958-2015. Applying corrections for elevation, bare ice albedo and accumulation bias, the high-resolution product is statistically downscaled from the native daily output of the polar regional climate model RACMO2.3 at 11 km. The data set includes all individual SMB components projected to a down-sampled version of the Greenland Ice Mapping Project (GIMP) digital elevation model and ice mask. The 1 km mask better resolves narrow ablation zones, valley glaciers, fjords and disconnected ice caps. Relative to the 11 km product, the more detailed representation of isolated glaciated areas leads to increased precipitation over the southeastern GrIS. In addition, the downscaled product shows a significant increase in runoff owing to better resolved low-lying marginal glaciated regions. The combined corrections for elevation and bare ice albedo markedly improve model agreement with a newly compiled data set of ablation measurements.

  15. Chemical composition, sources, and processes of urban aerosols during summertime in Northwest China: insights from High Resolution Aerosol Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    J. Xu

    2014-06-01

    Full Text Available An aerodyne High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS was deployed along with a Scanning Mobility Particle Sizer (SMPS and a Multi Angle Absorption Photometers (MAAP to measure the temporal variations of the mass loading, chemical composition, and size distribution of sub-micrometer particulate matter (PM1 in Lanzhou, northwest China, during 12 July–7 August 2012. The average PM1 mass concentration including non-refractory PM1 (NR-PM1 measured by HR-ToF-AMS and black carbon (BC measured by MAAP during this study was 24.5 μg m−3 (ranging from 0.86 to 105μg m−3, with a mean composition consisting of 47% organics, 16% sulfate, 12% BC, 11% ammonium, 10% nitrate, and 4% chloride. The organics was consisted of 70% carbon, 21% oxygen, 8% hydrogen, and 1% nitrogen, with the average oxygen-to-carbon ratio (O / C of 0.33 and organic mass-to-carbon ratio (OM / OC of 1.58. Positive matrix factorization (PMF of the high-resolution mass spectra of organic aerosols (OA identified four distinct factors which represent, respectively, two primary OA (POA emission sources (traffic and food cooking and two secondary OA (SOA types – a fresher, semi-volatile oxygenated OA (SV-OOA and a more aged, low-volatility oxygenated OA (LV-OOA. Traffic-related hydrocarbon-like OA (HOA and BC displayed distinct diurnal patterns both with peak at ~07:00–11:00 (BJT: UTC +8 corresponding to the morning rush hours, while cooking OA (COA peaked during three meal periods. The diurnal profiles of sulfate and LV-OOA displayed a broad peak between ∼07:00–15:00, while those of nitrate, ammonium, and SV-OOA showed a narrower peak at ~08:00–13:00. The later morning and early afternoon peak in the diurnal profiles of secondary aerosol species was likely caused by mixing down of pollutants aloft, which were likely produced in the residual layer decoupled from the boundary layer during night time. The mass spectrum of SV-OOA also showed similarity

  16. Arbitrary Angular Momentum Electron Repulsion Integrals with Graphical Processing Units: Application to the Resolution of Identity Hartree-Fock Method.

    Science.gov (United States)

    Kalinowski, Jaroslaw; Wennmohs, Frank; Neese, Frank

    2017-07-11

    A resolution of identity based implementation of the Hartree-Fock method on graphical processing units (GPUs) is presented that is capable of handling basis functions with arbitrary angular momentum. For practical reasons, only functions up to (ff|f) angular momentum are presently calculated on the GPU, thus leaving the calculation of higher angular momenta integrals on the CPU of the hybrid CPU-GPU environment. Speedups of up to a factor of 30 are demonstrated relative to state-of-the-art serial and parallel CPU implementations. Benchmark calculations with over 3500 contracted basis functions (def2-SVP or def2-TZVP basis sets) are reported. The presented implementation supports all devices with OpenCL support and is capable of utilizing multiple GPU cards over either MPI or OpenCL itself.

  17. UNITED NATION'S RESOLUTION ON ELIMINATION OF FEMALE GENITAL RITUAL: A LEGITIMATE RESPONSE TO A HUMAN RIGHTS PROBLEM OR WHAT?

    Science.gov (United States)

    Nnamuchi, Obiajulu

    2014-12-01

    A recent United Nations' (U.N.) Resolution, "Intensifying Global Efforts for the Elimination of Female Genital Mutilations," urging all countries to enact legislation outlawing female circumcision or female genital ritual (FGR) signals a disturbingly new frontier in the polemic surrounding the ancient cultural practice. Never before has the apex global institution lent its imprimatur to a project whose foundation is profoundly muddled in uncertainties and murkiness. That the Resolution received an instantaneous and near-universal acclaim as a necessary protective weapon against supposed assault on the human rights of women is not news. After all, aside from essentially validating extant legislative frameworks in several countries, the proclamation fits seamlessly with decades-long agitations of activists, scholars and media pundits of one stripe or the other. What is absurd--indeed, the real news--is continued neglect of calls for a rethinking of the criminalization fervor currently gripping the world, for a reassessment of the evidence trumpeted by abolitionists as justificatory of their unbridled interference in what practicing communities revere as a sacred cultural rite. Relying on the premise that claims regarding harmful impact of FGR, the fulcrum upon which eradication forces depend for their activism, cannot be substantiated, this paper argues that prohibitory regimes based thereon, whether at the U.N. or country level, is per se a violation of the human rights of the women purportedly sought to be protected. Human rights (including, in this case, its self-appointed "apostles"), cannot, as a popular Igbo maxim admonishes, become "outsiders who wept louder than the bereaved." This is the prism from which this paper analyzes the on-going supranational crusade to suppress FGR. It is a critique of extant FGR legal and policy regimes, an instance of which is the U.N. Resolution, as unrepresentative of legitimate advancement of human rights.

  18. Feasibility of the detection of trace elements in particulate matter using online High-Resolution Aerosol Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Salcedo, D.; Laskin, Alexander; Shutthanandan, V.; Jimenez, Jose L.

    2012-08-10

    The feasibility of using an online thermal-desorption electron-ionization high-resolution aerosol mass spectrometer (AMS) for the detection of particulate trace elements was investigated analyzing data from Mexico City obtained during the MILAGRO 2006 field campaign, where relatively high concentrations of trace elements have been reported. This potential application is of interest due to the real-time data provided by the AMS, its high sensitivity and time resolution, and the widespread availability and use of this instrument. High resolution mass spectral analysis, isotopic ratios, and ratios of different ions containing the same elements are used to constrain the chemical identity of the measured ions. The detection of Cu, Zn, As, Se, Sn, and Sb is reported. There was no convincing evidence for the detection of other trace elements commonly reported in PM. The elements detected tend to be those with lower melting and boiling points, as expected given the use of a vaporizer at 600oC in this instrument. Operation of the AMS vaporizer at higher temperatures is likely to improve trace element detection. The detection limit is estimated at approximately 0.3 ng m-3 for 5-min of data averaging. Concentration time series obtained from the AMS data were compared to concentration records determined from offline analysis of particle samples from the same times and locations by ICP (PM2.5) and PIXE (PM1.1 and PM0.3). The degree of correlation and agreement between the three instruments (AMS, ICP, and PIXE) varied depending on the element. The AMS shows promise for real-time detection of some trace elements, although additional work including laboratory calibrations with different chemical forms of these elements are needed to further develop this technique and to understand the differences with the ambient data from the other techniques. The trace elements peaked in the morning as expected for primary sources, and the many detected plumes suggest the presence of multiple

  19. Optimized ultra performance liquid chromatography tandem high resolution mass spectrometry method for the quantification of paraquat in plasma and urine.

    Science.gov (United States)

    Lu, Haihua; Yu, Jing; Wu, Linlin; Xing, Jingjing; Wang, Jun; Huang, Peipei; Zhang, Jinsong; Xiao, Hang; Gao, Rong

    2016-08-01

    A simple, sensitive and specific ultra performance liquid chromatography coupled to electrospray tandem high resolution mass spectrometry (UPLC-ESI-HRMS/MS) method has been developed and validated for quantification of paraquat in plasma and urine. The sample preparation was carried out by one-step protein precipitation with acetonitrile. The paraquat was separated with a HILIC column in 10min. Detection was performed using Q Exactive Orbitrap mass spectrometer by Targeted-MS/MS scan mode. Methodological parameters, such as ammonium formate concentration, formic acid concentration, spray voltage, capillary temperature, heater temperature and normalized collision energy were optimized to achieve the highest sensitivity. The calibration curve was linear over the concentration range of LOQ-1000ng/mL. LOD was 0.1 and 0.3ng/mL, LOQ was 0.3 and 0.8ng/mL for urine and plasma, respectively. The intra- and inter-day precisions were paraquat concentration in plasma samples with hemoperfusion from 5 suspected paraquat poisoning patients.

  20. Oligomers, organosulfates, and nitrooxy organosulfates in rainwater identified by ultra-high resolution electrospray ionization FT-ICR mass spectrometry

    Science.gov (United States)

    Altieri, K. E.; Turpin, B. J.; Seitzinger, S. P.

    2009-04-01

    Wet deposition is an important removal mechanism for atmospheric organic matter, and a potentially important input for receiving ecosystems, yet less than 50% of rainwater organic matter is considered chemically characterized. Precipitation samples collected in New Jersey, USA, were analyzed by negative ion ultra-high resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Elemental compositions of 552 unique molecular species were determined in the mass range 50-500 Da in the rainwater. Four main groups of organic compounds were identified: compounds containing carbon, hydrogen, and oxygen (CHO) only, sulfur (S) containing CHOS compounds, nitrogen (N) containing CHON compounds, and S- and N- containing CHONS compounds. Organic acids commonly identified in precipitation were detected in the rainwater. Within the four main groups of compounds detected in the rainwater, oligomers, organosulfates, and nitrooxy-organosulfates were assigned based on elemental formula comparisons. The majority of the compounds identified are products of atmospheric reactions and are known contributors to secondary organic aerosol (SOA) formed from gas phase, aerosol phase, and in-cloud reactions in the atmosphere. It is suggested that the large uncharacterized component of SOA is the main contributor to the large uncharacterized component of rainwater organic matter.

  1. Qualitative and quantitative analysis of Andrographis paniculata by rapid resolution liquid chromatography/time-of-flight mass spectrometry.

    Science.gov (United States)

    Song, Yong-Xi; Liu, Shi-Ping; Jin, Zhao; Qin, Jian-Fei; Jiang, Zhi-Yuan

    2013-09-30

    A rapid resolution liquid chromatography/time-of-flight tandem mass spectrometry (RRLC-TOF/MS) method was developed for qualitative and quantitative analysis of the major chemical constituents in Andrographis paniculata. Fifteen compounds, including flavonoids and diterpenoid lactones, were unambiguously or tentatively identified in 10 min by comparing their retention times and accurate masses with standards or literature data. The characteristic fragmentation patterns of flavonoids and diterpenoid lactones were summarized, and the structures of the unknown compounds were predicted. Andrographolide, dehydroandrographolide and neoandrographolide were further quantified as marker substances. It was found that the calibration curves for all analytes showed good linearity (R² > 0.9995) within the test ranges. The overall limits of detection (LODs) and limits of quantification (LOQs) were 0.02 μg/mL to 0.06 μg/mL and 0.06 μg/mL to 0.2 μg/mL, respectively. The relative standard deviations (RSDs) for intra- and inter-day precisions were below 3.3% and 4.2%, respectively. The mean recovery rates ranged from 96.7% to 104.5% with the relative standard deviations (RSDs) less than 2.72%. It is concluded that RRLC-TOF/MS is powerful and practical in qualitative and quantitative analysis of complex plant samples due to time savings, sensitivity, precision, accuracy and lowering solvent consumption.

  2. Investigation of pharmaceuticals in processed animal by-products by liquid chromatography coupled to high-resolution mass spectrometry.

    Science.gov (United States)

    Nácher-Mestre, Jaime; Ibáñez, María; Serrano, Roque; Boix, Clara; Bijlsma, Lubertus; Lunestad, Bjørn Tore; Hannisdal, Rita; Alm, Martin; Hernández, Félix; Berntssen, Marc H G

    2016-07-01

    There is an on-going trend for developing more sustainable salmon feed in which traditionally applied marine feed ingredients are replaced with alternatives. Processed animal products (PAPs) have been re-authorized as novel high quality protein ingredients in 2013. These PAPs may harbor undesirable substances such as pharmaceuticals and metabolites which are not previously associated with salmon farming, but might cause a potential risk for feed and food safety. To control these contaminants, an analytical strategy based on a generic extraction followed by ultra-high performance liquid chromatography coupled to high resolution mass spectrometry (UHPLC-HRMS) using quadrupole time-of-flight mass analyzer (QTOF MS) was applied for wide scope screening. Quality control samples, consisting of PAP commodities spiked at 0.02, 0.1 and 0.2 mg/kg with 150 analytes, were injected in every sample batch to verify the overall method performance. The methodology was applied to 19 commercially available PAP samples from six different types of matrices from the EU animal rendering industry. This strategy allows assessing possible emergent risk exposition of the salmon farming industry to 1005 undesirables, including pharmaceuticals, several dyes and relevant metabolites.

  3. Retrospective screening of pesticide metabolites in ambient air using liquid chromatography coupled to high-resolution mass spectrometry.

    Science.gov (United States)

    López, Antonio; Yusà, Vicent; Millet, Maurice; Coscollà, Clara

    2016-04-01

    A new methodology for the retrospective screening of pesticide metabolites in ambient air was developed, using liquid chromatography coupled to Orbitrap high-resolution mass spectrometry (UHPLC-HRMS), including two systematic workflows (i) post-run target screening (suspect screening) and (ii) non-target screening. An accurate-mass database was built and used for the post-run screening analysis. The database contained 240 pesticide metabolites found in different matrixes such as air, soil, water, plants, animals and humans. For non-target analysis, a "fragmentation-degradation" relationship strategy was selected. The proposed methodology was applied to 31 air samples (PM10) collected in the Valencian Region (Spain). In the post-target analysis 34 metabolites were identified, of which 11 (3-ketocarburan, carbofuran-7-phenol, carbendazim, desmethylisoproturon, ethiofencarb-sulfoxide, malaoxon, methiocarb-sulfoxide, N-(2-ethyl-6-methylphenyl)-L-alanine, omethoate, 2-hydroxy-terbuthylazine, and THPAM) were confirmed using analytical standards. The semiquantitative estimated concentration ranged between 6.78 and 198.31 pg m(-3). Likewise, two unknown degradation products of malaoxon and fenhexamid were elucidated in the non-target screening.

  4. Retrospective analysis of pesticide metabolites in urine using liquid chromatography coupled to high-resolution mass spectrometry.

    Science.gov (United States)

    López, Antonio; Dualde, Pablo; Yusà, Vicent; Coscollà, Clara

    2016-11-01

    A comprehensive retrospective analysis of pesticide metabolites in urine was developed, using liquid chromatography coupled to Orbitrap high-resolution mass spectrometry (UHPLC-HRMS) that includes both post-run target (suspect screening) and non-target screening. An accurate-mass database comprising 263 pesticide metabolites was built and used for the post-run screening analysis. For non-target analysis, a "fragmentation-degradation" relationship strategy was selected. The proposed methodology was applied to 49 real urine samples from pregnant women. In the post-target analysis 26 pesticide metabolites were tentatively identified, 8 of which (2-diethylamino-6-methyl-pyrimidinol; 3-ketocarbofuran; 4,6-dimethoxy-2-pyrimidinamine; 4-hydroxy-2-isporopyl-6-methylpyrimidine; diethyl malate; diethyl maleate; N-(2-Ethyl-6-methylphenyl)-2-hydroxyacetamide and propachlor oxanilic acid ) were confirmed using analytical standards. Likewise, one unknown degradation product, methyl-N-phenylcarbamate was elucidated in the non-target screening. Finally, the real urine samples were grouped according to their origin applying a metabolomic approach.

  5. Qualitative and Quantitative Analysis of Andrographis paniculata by Rapid Resolution Liquid Chromatography/Time-of-Flight Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Jian-Fei Qin

    2013-09-01

    Full Text Available A rapid resolution liquid chromatography/time-of-flight tandem mass spectrometry (RRLC-TOF/MS method was developed for qualitative and quantitative analysis of the major chemical constituents in Andrographis paniculata. Fifteen compounds, including flavonoids and diterpenoid lactones, were unambiguously or tentatively identified in 10 min by comparing their retention times and accurate masses with standards or literature data. The characteristic fragmentation patterns of flavonoids and diterpenoid lactones were summarized, and the structures of the unknown compounds were predicted. Andrographolide, dehydroandrographolide and neoandrographolide were further quantified as marker substances. It was found that the calibration curves for all analytes showed good linearity (R2 > 0.9995 within the test ranges. The overall limits of detection (LODs and limits of quantification (LOQs were 0.02 μg/mL to 0.06 μg/mL and 0.06 μg/mL to 0.2 μg/mL, respectively. The relative standard deviations (RSDs for intra- and inter-day precisions were below 3.3% and 4.2%, respectively. The mean recovery rates ranged from 96.7% to 104.5% with the relative standard deviations (RSDs less than 2.72%. It is concluded that RRLC-TOF/MS is powerful and practical in qualitative and quantitative analysis of complex plant samples due to time savings, sensitivity, precision, accuracy and lowering solvent consumption.

  6. Measurement of the Black Hole Mass in NGC 1332 from ALMA Observations at 0.044 arcsecond Resolution

    Science.gov (United States)

    Barth, Aaron J.; Boizelle, Benjamin D.; Darling, Jeremy; Baker, Andrew J.; Buote, David A.; Ho, Luis C.; Walsh, Jonelle L.

    2016-05-01

    We present Atacama Large Millimeter/submillimeter Array (ALMA) Cycle 3 observations of CO(2-1) emission from the circumnuclear disk in the E/S0 galaxy NGC 1332 at 0.″044 resolution. The disk exhibits regular rotational kinematics and central high-velocity emission (±500 km s-1) consistent with the presence of a compact central mass. We construct models for a thin, dynamically cold disk in the gravitational potential of the host galaxy and black hole and fit the beam-smeared model line profiles directly to the ALMA data cube. Model fits successfully reproduce the disk kinematics out to r = 200 pc. Fitting models just to spatial pixels within projected r = 50 pc of the nucleus (two times larger than the black hole’s gravitational radius of influence), we find {M}{BH}=({6.64}-0.63+0.65)× {10}8 {M}⊙ . This observation demonstrates ALMA’s powerful capability to determine the masses of supermassive black holes by resolving gas kinematics on small angular scales in galaxy nuclei.

  7. High molecular weight SOA formation during limonene ozonolysis: insights from ultrahigh-resolution FT-ICR mass spectrometry characterization

    Science.gov (United States)

    Kundu, S.; Fisseha, R.; Putman, A. L.; Rahn, T. A.; Mazzoleni, L. R.

    2012-06-01

    The detailed molecular composition of laboratory generated limonene ozonolysis secondary organic aerosol (SOA) was studied using ultrahigh-resolution Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Approximately 1200 molecular formulas were identified in the SOA over the mass range of 140 to 850 Da. Four characteristic groups of high relative abundance species were observed; they indicate an array of accretion products that retain a large fraction of the limonene skeleton. The identified molecular formulas of each of the groups are related to one another by CH2, O and CH2O homologous series. The CH2 and O homologous series of the low molecular weight (MW) SOA (m/z z > 300) were found to constitute a significant number fraction of the identified SOA components. The formation of high MW compounds was evaluated by molecular formula trends, fragmentation analysis of select high MW compounds and a comprehensive reaction matrix including the identified low MW SOA, hydroperoxides and Criegee radicals as building blocks. Although the formation of high MW SOA may occur via a variety of radical and non-radical reaction channels, the combined approach indicates a greater importance of the non-condensation reactions over aldol and ester condensation reaction channels. Among these hemi-acetal reactions appear to be most dominant followed by hydroperoxide and Criegee reaction channels.

  8. Oligomers, organosulfates, and nitrooxy organosulfates in rainwater identified by ultra-high resolution electrospray ionization FT-ICR mass spectrometry

    Directory of Open Access Journals (Sweden)

    K. E. Altieri

    2009-04-01

    Full Text Available Wet deposition is an important removal mechanism for atmospheric organic matter, and a potentially important input for receiving ecosystems, yet less than 50% of rainwater organic matter is considered chemically characterized. Precipitation samples collected in New Jersey, USA, were analyzed by negative ion ultra-high resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS. Elemental compositions of 552 unique molecular species were determined in the mass range 50–500 Da in the rainwater. Four main groups of organic compounds were identified: compounds containing carbon, hydrogen, and oxygen (CHO only, sulfur (S containing CHOS compounds, nitrogen (N containing CHON compounds, and S- and N- containing CHONS compounds. Organic acids commonly identified in precipitation were detected in the rainwater. Within the four main groups of compounds detected in the rainwater, oligomers, organosulfates, and nitrooxy-organosulfates were assigned based on elemental formula comparisons. The majority of the compounds identified are products of atmospheric reactions and are known contributors to secondary organic aerosol (SOA formed from gas phase, aerosol phase, and in-cloud reactions in the atmosphere. It is suggested that the large uncharacterized component of SOA is the main contributor to the large uncharacterized component of rainwater organic matter.

  9. First characterization of AKB-48 metabolism, a novel synthetic cannabinoid, using human hepatocytes and high-resolution mass spectrometry.

    Science.gov (United States)

    Gandhi, Adarsh S; Zhu, Mingshe; Pang, Shaokun; Wohlfarth, Ariane; Scheidweiler, Karl B; Liu, Hua-Fen; Huestis, Marilyn A

    2013-10-01

    Since the federal authorities scheduled the first synthetic cannabinoids, JWH-018 and JWH-073, new synthetic cannabinoids were robustly marketed. N-(1-Adamantyl)-1-pentylindazole-3-carboxamide (AKB-48), also known as APINACA, was recently observed in Japanese herbal smoking blends. The National Forensic Laboratory Information System registered 443 reports of AKB-48 cases in the USA from March 2010 to January 2013. In May 2013, the Drug Enforcement Administration listed AKB-48 as a Schedule I drug. Recently, AKB-48 was shown to have twice the CB1 receptor binding affinity than CB2. These pharmacological effects and the difficulty in detecting the parent compound in urine highlight the importance of metabolite identification for developing analytical methods for clinical and forensic investigations. Using human hepatocytes and TripleTOF mass spectrometry, we identified 17 novel phase I and II AKB-48 metabolites, products of monohydroxylation, dihydroxylation, or trihydroxylation on the aliphatic adamantane ring or N-pentyl side chain. Glucuronide conjugation of some mono- and dihydroxylated metabolites also occurred. Oxidation and dihydroxylation on the adamantane ring and N-pentyl side chain formed a ketone. More metabolites were identified after 3 h of incubation than at 1 h. For the first time, we present a AKB-48 metabolic scheme obtained from human hepatocytes and high-resolution mass spectrometry. These data are needed to develop analytical methods to identify AKB-48 consumption in clinical and forensic testing.

  10. A new method to discriminate secondary organic aerosols from different sources using high-resolution aerosol mass spectra

    Science.gov (United States)

    Heringa, M. F.; Decarlo, P. F.; Chirico, R.; Tritscher, T.; Clairotte, M.; Mohr, C.; Crippa, M.; Slowik, J. G.; Pfaffenberger, L.; Dommen, J.; Weingartner, E.; Prévôt, A. S. H.; Baltensperger, U.

    2012-02-01

    Organic aerosol (OA) represents a significant and often major fraction of the non-refractory PM1 (particulate matter with an aerodynamic diameter da car and a two-stroke Euro 2 scooter were characterized with an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS) and compared to SOA from α-pinene. The emissions were sampled from the chimney/tailpipe by a heated inlet system and filtered before injection into a smog chamber. The gas phase emissions were irradiated by xenon arc lamps to initiate photo-chemistry which led to nucleation and subsequent particle growth by SOA production. Duplicate experiments were performed for each SOA type, with the averaged organic mass spectra showing Pearson's r values >0.94 for the correlations between the four different SOA types after five hours of aging. High-resolution mass spectra (HR-MS) showed that the dominant peaks in the MS, m/z 43 and 44, are dominated by the oxygenated ions C2H3O+ and CO2+, respectively, similarly to the relatively fresh semi-volatile oxygenated OA (SV-OOA) observed in the ambient aerosol. The atomic O:C ratios were found to be in the range of 0.25-0.55 with no major increase during the first five hours of aging. On average, the diesel SOA showed the lowest O:C ratio followed by SOA from wood burning, α-pinene and the scooter emissions. Grouping the fragment ions revealed that the SOA source with the highest O:C ratio had the largest fraction of small ions. The HR data of the four sources could be clustered and separated using principal component analysis (PCA). The model showed a significant separation of the four SOA types and clustering of the duplicate experiments on the first two principal components (PCs), which explained 79% of the total variance. Projection of ambient SV-OOA spectra resolved by positive matrix factorization (PMF) showed that this approach could be useful to identify large contributions of the tested SOA sources to SV-OOA. The first results from this

  11. Molecular characterization of water soluble organic nitrogen in marine rainwater by ultra-high resolution electrospray ionization mass spectrometry

    Science.gov (United States)

    Altieri, K. E.; Hastings, M. G.; Peters, A. J.; Sigman, D. M.

    2012-04-01

    Atmospheric water soluble organic nitrogen (WSON) is a subset of the complex organic matter in aerosols and rainwater, which impacts cloud condensation processes and aerosol chemical and optical properties and may play a significant role in the biogeochemical cycle of N. However, its sources, composition, connections to inorganic N, and variability are largely unknown. Rainwater samples were collected on the island of Bermuda (32.27° N, 64.87° W), which experiences both anthropogenic and marine influenced air masses. Samples were analyzed by ultra-high resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry to chemically characterize the WSON. Elemental compositions of 2281 N containing compounds were determined over the mass range m/z+ 50 to 500. The five compound classes with the largest number of elemental formulas identified, in order from the highest number of formulas to the lowest, contained carbon, hydrogen, oxygen, and nitrogen (CHON+), CHON compounds that contained sulfur (CHONS+), CHON compounds that contained phosphorus (CHONP+), CHON compounds that contained both sulfur and phosphorus (CHONSP+), and compounds that contained only carbon, hydrogen, and nitrogen (CHN+). Compared to rainwater collected in the continental USA, average O:C ratios of all N containing compound classes were lower in the marine samples whereas double bond equivalent values were higher, suggesting a reduced role of secondary formation mechanisms. Despite their prevalence in continental rainwater, no organonitrates or nitrooxy-organosulfates were detected, but there was an increased presence of organic S and organic P containing compounds in the marine rainwater. Cluster analysis showed a clear chemical distinction between samples collected during the cold season (October to March) which have anthropogenic air mass origins and samples collected during the warm season (April to September) with remote marine air mass origins. This, in

  12. Molecular characterization of water soluble organic nitrogen in marine rainwater by ultra-high resolution electrospray ionization mass spectrometry

    Directory of Open Access Journals (Sweden)

    K. E. Altieri

    2011-11-01

    Full Text Available Atmospheric water soluble organic nitrogen (WSON is a subset of the complex organic matter in aerosols and rainwater, which impacts cloud condensation processes and aerosol chemical and optical properties, and may play a significant role in the biogeochemical cycle of N. However, its sources, composition, connections to inorganic N, and variability are largely unknown. Rainwater samples were collected on the island of Bermuda (32.27° N, 64.87° W, which experiences both anthropogenic and marine influenced air masses. Samples were analyzed by ultra-high resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry to chemically characterize the WSON. Elemental compositions of 2455 N containing compounds were determined over the mass range m/z+ 50 to 500. The five compound classes with the largest number of elemental formulas identified, in order from the highest number of formulas to the lowest, contained carbon, hydrogen, oxygen, and nitrogen (CHON+, CHON compounds that contained sulfur (CHONS+, CHON compounds that contained phosphorous (CHONP+, CHON compounds that contained both sulfur and phosphorous (CHONSP+, and compounds that contained only carbon, hydrogen, and nitrogen (CHN+. No organonitrates or nitrooxy-organosulfates were detected, but there was an increased presence of organic S and organic P containing compounds in the marine rainwater. Compared to rainwater collected in the continental USA, average O:C ratios of all N containing compound classes were lower in the marine samples whereas double bond equivalent values were higher, suggesting a reduced role of secondary formation mechanisms. Cluster analysis showed a clear chemical distinction between samples collected during the cold season (October to March which have anthropogenic air mass origins and samples collected during the warm season (April to September with remote marine air mass origins. This, in conjunction with patterns

  13. Balancing the false negative and positive rates in suspect screening with high-resolution Orbitrap mass spectrometry using multivariate statistics.

    Science.gov (United States)

    Vergeynst, Leendert; Van Langenhove, Herman; Demeestere, Kristof

    2015-02-17

    Modern high-resolution mass spectrometry (HRMS) enables full-spectrum trace level analysis of emerging environmental organic contaminants. This raises the opportunity for post-acquisition suspect screening when no reference standards are a priori available. When setting up a conventional screening identification train based on successively different identification criteria including mass error and isotope fit, the false negative rate typically accumulates upon advancing through the decision tree. The challenge is thus to elaborate a well-balanced screening, in which the different criteria are equally stringent, leading to a controllable number of false negatives. Presented is a novel suspect screening approach using liquid-chromatography Orbitrap HRMS. Based on a multivariate statistical model, the screening takes into account the accurate mass error of the mono isotopic ion and up to three isotopes, isotope ratios, and a peak/noise filter. As such, for the first time, controlling the overall false negative rate of the screening algorithm to a desired level (5% in this study) is achieved. Simultaneously, a well-balanced identification decision is guaranteed taking the different identification criteria as a whole in a holistic statistical approach. Taking into account 1, 2, and 3 isotopes decreases the false positive rate from 22, 2.8 to <0.3%, but the cost of increasing the median limits of identification from 200, 2000 to 2062 ng L(-1), respectively, should also be considered. As proof of concept, 7 biologically treated wastewaters were screened toward 77 suspect pharmaceuticals resulting in the indicative identification of 25 suspects. Subsequently obtained reference standards allowed confirmation for 19 out of these 25 pharmaceutical contaminants.

  14. The expression profile of phosphatidylinositol in high spatial resolution imaging mass spectrometry as a potential biomarker for prostate cancer.

    Directory of Open Access Journals (Sweden)

    Takayuki Goto

    Full Text Available High-resolution matrix-assisted laser desorption/ionization imaging mass spectrometry (HR-MALDI-IMS is an emerging application for the comprehensive and detailed analysis of the spatial distribution of ionized molecules in situ on tissue slides. HR-MALDI-IMS in negative mode in a mass range of m/z 500-1000 was performed on optimal cutting temperature (OCT compound-embedded human prostate tissue samples obtained from patients with prostate cancer at the time of radical prostatectomy. HR-MALDI-IMS analysis of the 14 samples in the discovery set identified 26 molecules as highly expressed in the prostate. Tandem mass spectrometry (MS/MS showed that these molecules included 14 phosphatidylinositols (PIs, 3 phosphatidylethanolamines (PEs and 3 phosphatidic acids (PAs. Among the PIs, the expression of PI(18:0/18:1, PI(18:0/20:3 and PI(18:0/20:2 were significantly higher in cancer tissue than in benign epithelium. A biomarker algorithm for prostate cancer was formulated by analyzing the expression profiles of PIs in cancer tissue and benign epithelium of the discovery set using orthogonal partial least squares discriminant analysis (OPLS-DA. The sensitivity and specificity of this algorithm for prostate cancer diagnosis in the 24 validation set samples were 87.5 and 91.7%, respectively. In conclusion, HR-MALDI-IMS identified several PIs as being more highly expressed in prostate cancer than benign prostate epithelium. These differences in PI expression profiles may serve as a novel diagnostic tool for prostate cancer.

  15. Multi-Wire Tri-Gate Silicon Nanowires Reaching Milli-pH Unit Resolution in One Micron Square Footprint.

    Science.gov (United States)

    Accastelli, Enrico; Scarbolo, Paolo; Ernst, Thomas; Palestri, Pierpaolo; Selmi, Luca; Guiducci, Carlotta

    2016-03-15

    The signal-to-noise ratio of planar ISFET pH sensors deteriorates when reducing the area occupied by the device, thus hampering the scalability of on-chip analytical systems which detect the DNA polymerase through pH measurements. Top-down nano-sized tri-gate transistors, such as silicon nanowires, are designed for high performance solid-state circuits thanks to their superior properties of voltage-to-current transduction, which can be advantageously exploited for pH sensing. A systematic study is carried out on rectangular-shaped nanowires developed in a complementary metal-oxide-semiconductor (CMOS)-compatible technology, showing that reducing the width of the devices below a few hundreds of nanometers leads to higher charge sensitivity. Moreover, devices composed of several wires in parallel further increase the exposed surface per unit footprint area, thus maximizing the signal-to-noise ratio. This technology allows a sub milli-pH unit resolution with a sensor footprint of about 1 µm², exceeding the performance of previously reported studies on silicon nanowires by two orders of magnitude.

  16. Multi-Wire Tri-Gate Silicon Nanowires Reaching Milli-pH Unit Resolution in One Micron Square Footprint

    Directory of Open Access Journals (Sweden)

    Enrico Accastelli

    2016-03-01

    Full Text Available The signal-to-noise ratio of planar ISFET pH sensors deteriorates when reducing the area occupied by the device, thus hampering the scalability of on-chip analytical systems which detect the DNA polymerase through pH measurements. Top-down nano-sized tri-gate transistors, such as silicon nanowires, are designed for high performance solid-state circuits thanks to their superior properties of voltage-to-current transduction, which can be advantageously exploited for pH sensing. A systematic study is carried out on rectangular-shaped nanowires developed in a complementary metal-oxide-semiconductor (CMOS-compatible technology, showing that reducing the width of the devices below a few hundreds of nanometers leads to higher charge sensitivity. Moreover, devices composed of several wires in parallel further increase the exposed surface per unit footprint area, thus maximizing the signal-to-noise ratio. This technology allows a sub milli-pH unit resolution with a sensor footprint of about 1 µm2, exceeding the performance of previously reported studies on silicon nanowires by two orders of magnitude.

  17. Triple Quadrupole Versus High Resolution Quadrupole-Time-of-Flight Mass Spectrometry for Quantitative LC-MS/MS Analysis of 25-Hydroxyvitamin D in Human Serum

    Science.gov (United States)

    Geib, Timon; Sleno, Lekha; Hall, Rabea A.; Stokes, Caroline S.; Volmer, Dietrich A.

    2016-08-01

    We describe a systematic comparison of high and low resolution LC-MS/MS assays for quantification of 25-hydroxyvitamin D3 in human serum. Identical sample preparation, chromatography separations, electrospray ionization sources, precursor ion selection, and ion activation were used; the two assays differed only in the implemented final mass analyzer stage; viz. high resolution quadrupole-quadrupole-time-of-flight (QqTOF) versus low resolution triple quadrupole instruments. The results were assessed against measured concentration levels from a routine clinical chemiluminescence immunoassay. Isobaric interferences prevented the simple use of TOF-MS spectra for extraction of accurate masses and necessitated the application of collision-induced dissociation on the QqTOF platform. The two mass spectrometry assays provided very similar analytical figures of merit, reflecting the lack of relevant isobaric interferences in the MS/MS domain, and were successfully applied to determine the levels of 25-hydroxyvitamin D for patients with chronic liver disease.

  18. Fabrication of High Resolution Lightweight X-ray Mirrors Using Mono-crystalline Silicon Project

    Data.gov (United States)

    National Aeronautics and Space Administration — "Three factors characterize an X-ray optics fabrication technology: angular resolution, effective area per unit mass, and production cost per unit effective...

  19. Atmospheric-pressure chemical ionization tandem mass spectrometry (APGC/MS/MS) an alternative to high-resolution mass spectrometry (HRGC/HRMS) for the determination of dioxins.

    Science.gov (United States)

    van Bavel, Bert; Geng, Dawei; Cherta, Laura; Nácher-Mestre, Jaime; Portolés, Tania; Ábalos, Manuela; Sauló, Jordi; Abad, Esteban; Dunstan, Jody; Jones, Rhys; Kotz, Alexander; Winterhalter, Helmut; Malisch, Rainer; Traag, Wim; Hagberg, Jessika; Ericson Jogsten, Ingrid; Beltran, Joaquim; Hernández, Félix

    2015-09-01

    The use of a new atmospheric-pressure chemical ionization source for gas chromatography (APGC) coupled with a tandem quadrupole mass spectrometry (MS/MS) system, as an alternative to high-resolution mass spectrometry (HRMS), for the determination of PCDDs/PCDFs is described. The potential of using atmospheric-pressure chemical ionization (APCI) coupled to a tandem quadrupole analyzer has been validated for the identification and quantification of dioxins and furans in different complex matrices. The main advantage of using the APCI source is the soft ionization at atmospheric pressure, which results in very limited fragmentation. APCI mass spectra are dominated by the molecular ion cluster, in contrast with the high energy ionization process under electron ionization (EI). The use of the molecular ion as the precursor ion in MS/MS enhances selectivity and, consequently, sensitivity by increasing the signal-to-noise ratios (S/N). For standard solutions of 2,3,7,8-TCDD, injections of 10 fg in the splitless mode on 30- or 60-m-length, 0.25 mm inner diameter (id), and 25 μm film thickness low-polarity capillary columns (DB5MS type), signal-to-noise (S/N) ratios of >10:1 were routinely obtained. Linearity was achieved in the region (correlation coefficient of r(2) > 0.998) for calibration curves ranging from 100 fg/μL to 1000 pg/μL. The results from a wide variety of complex samples, including certified and standard reference materials and samples from several QA/QC studies, which were previously analyzed by EI HRGC/HRMS, were compared with the results from the APGC/MS/MS system. Results between instruments showed good agreement both in individual congeners and toxic equivalence factors (TEQs). The data show that the use of APGC in combination with MS/MS for the analysis of dioxins has the same potential, in terms of sensitivity and selectivity, as the traditional HRMS instrumentation used for this analysis. However, the APCI/MS/MS system, as a benchtop system, is

  20. Thermoregulation in boys and men exercising at the same heat production per unit body mass.

    Science.gov (United States)

    Leites, Gabriela T; Cunha, Giovani S; Obeid, Joyce; Wilk, Boguslaw; Meyer, Flavia; Timmons, Brian W

    2016-07-01

    Child-adult thermoregulatory comparisons may be biased by differences in metabolic heat production ([Formula: see text]). We compared thermoregulatory responses of boys and men exercising at two intensities prescribed to elicit either a fixed [Formula: see text] per unit body mass (BM) or a fixed absolute [Formula: see text]. Ten boys (10-12 years) and 10 men (19-25 years) performed 4 × 20-min cycling at a fixed [Formula: see text] per BM (W kg(-1)) at 35 °C and 35 % relative humidity (MENREL). Men also cycled (MENABS) at the same absolute [Formula: see text] (in W) as the boys. [Formula: see text] was lower in boys compared with MENREL, but similar to MENABS (mean ± SD, 233.6 ± 38.4, 396.5 ± 72.3, 233.6 ± 34.1 W, respectively, P < 0.001). Conversely, [Formula: see text] per unit BM was similar between boys and MENREL, and lower in MENABS (5.7 ± 1.0, 5.6 ± 0.8 and 3.3 ± 0.3 W kg(-1), respectively; P < 0.001). The change in rectal temperature was similar between boys and MENREL (0.6 ± 0.2 vs. 0.7 ± 0.2 °C, P = 0.92) but was lower in MENABS (0.3 ± 0.2 °C, P = 0.004). Sweat volume was lower in boys compared to MENABS (500 ± 173 vs. 710 ± 150 mL; P = 0.041), despite the same evaporative heat balance requirement (E req) (199.1 ± 34.2 vs. 201.0 ± 32.7 W, P = 0.87). Boys and men demonstrated similar thermoregulatory responses to 80 min of exercise in the heat performed at a fixed [Formula: see text] per unit BM. Sweat volume was lower in boys compared to men, despite similarities in absolute [Formula: see text] and E req.

  1. Final Technical Report for DE-FG02-06ER15835: Chemical Imaging with 100nm Spatial Resolution: Combining High Resolution Flurosecence Microscopy and Ion Mobility Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Buratto, Steven K. [UC Santa Barbara

    2013-09-03

    We have combined, in a single instrument, high spatial resolution optical microscopy with the chemical specificity and conformational selectivity of ion mobility mass spectrometry. We discuss the design and construction of this apparatus as well as our efforts in applying this technique to thin films of molecular semiconductor materials.

  2. Chemical characterization of particle emissions from controlled burns of biomass fuels using a high resolution time-of-flight aerosol mass spectrometer

    Directory of Open Access Journals (Sweden)

    L. Qi

    2012-03-01

    Full Text Available A total of forty-nine burns were conducted at the Missoula Fire Sciences Lab consisting of nine fuel types; i.e., chamise scrub oak, ceanothus, maritime chaparral, coastal sage scrub, California sage brush, Manzanita, oak savanna, oak woodland and masticated mesquite. This paper focuses on the chemical characterization of fine particle emissions collected for flaming, mixed and smoldering phases using a HR ToF-AMS. The evolution of OM/OC, H/C, O/C and N/C from fire ignition to extinction was measured to capture the transient and integrated chemical composition of the non-refractory portion of bulk particles. Real time elemental ratios and empirical formulas derived with respect to modified combustion efficiency (MCE are reported. For each fuel, the hydrogen fragment ions dominate the unit mass resolution (UMR mass spectra with no specific fragment ions attributable to an individual ecological combination. An interference ion in the UMR m/z 73, a fragment normally attributed to levoglucosan, is noted. Therefore, the results imply that C2H4O2+ (m/z 60.021 plus C3H5O2+ (m/z 73.029 are more sufficient to estimate the contribution of levoglucosan. The results did not show significant variations of levoglucosan content in the organic particle with the overall average contribution fraction ranging from 0.74% for coastal sage to 1.93% for chamise.

  3. Validity of Ski Skating Center-of-Mass Displacement Measured by a Single Inertial Measurement Unit.

    Science.gov (United States)

    Myklebust, Håvard; Gløersen, Øyvind; Hallén, Jostein

    2015-12-01

    In regard to simplifying motion analysis and estimating center of mass (COM) in ski skating, this study addressed 3 main questions concerning the use of inertial measurement units (IMU): (1) How accurately can a single IMU estimate displacement of os sacrum (S1) on a person during ski skating? (2) Does incorporating gyroscope and accelerometer data increase accuracy and precision? (3) Moreover, how accurately does S1 determine COM displacement? Six world-class skiers roller-ski skated on a treadmill using 2 different subtechniques. An IMU including accelerometers alone (IMU-A) or in combination with gyroscopes (IMU-G) were mounted on the S1. A reflective marker at S1, and COM calculated from 3D full-body optical analysis, were used to provide reference values. IMU-A provided an accurate and precise estimate of vertical S1 displacement, but IMU-G was required to attain accuracy and precision of < 8 mm (root-mean-squared error and range of displacement deviation) in all directions and with both subtechniques. Further, arm and torso movements affected COM, but not the S1. Hence, S1 displacement was valid for estimating sideways COM displacement, but the systematic amplitude and timing difference between S1 and COM displacement in the anteroposterior and vertical directions inhibits exact calculation of energy fluctuations.

  4. Fast Airborne Aerosol Size and Chemistry Measurements with the High Resolution Aerosol Mass Spectrometer during the MILAGRO Campaign

    Science.gov (United States)

    DeCarlo, P. F.; Dunlea, E. J.; Kimmel, J. R.; Aiken, A. C.; Sueper, D.; Crounse, J.; Wennberg, P. O.; Emmons, L.; Shinozuka, Y.; Clarke, A.; Zhou, J.; Tomlinson, J.; Collins,D. R.; Knapp, D.; Weinheimer, A. J.; Montzka,D. D.; Campos,T.; Jimenez, J. L.

    2007-01-01

    The concentration, size, and composition of non-refractory submicron aerosol (NR-PM(sub l)) was measured over Mexico City and central Mexico with a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) onboard the NSF/NCAR C-130 aircraft as part of the MILAGRO field campaign. This was the first aircraft deployment of the HR-ToF-AMS. During the campaign the instrument performed very well, and provided 12 s data. The aerosol mass from the AMS correlates strongly with other aerosol measurements on board the aircraft. Organic aerosol (OA) species dominate the NR-PM(sub l) mass. OA correlates strongly with CO and HCN indicating that pollution (mostly secondary OA, SOA) and biomass burning (BB) are the main OA sources. The OA to CO ratio indicates a typical value for aged air of around 80 microg/cubic m (STP) ppm(exp -1). This is within the range observed in outflow from the Northeastern US, which could be due to a compensating effect between higher BB but lower biogenic VOC emissions during this study. The O/C atomic ratio for OA is calculated from the HR mass spectra and shows a clear increase with photochemical age, as SOA forms rapidly and quickly overwhelms primary urban OA, consistent with Volkamer et al. (2006) and Kleinman et al. (2008). The stability of the OA/CO while O/C increases with photochemical age implies a net loss of carbon from the OA. BB OA is marked by signals at m/z 60 and 73, and also by a signal enhancement at large m/z indicative of larger molecules or more resistance to fragmentation. The main inorganic components show different spatial patterns and size distributions. Sulfate is regional in nature with clear volcanic and petrochemical/power plant sources, while the urban area is not a major regional source for this species. Nitrate is enhanced significantly in the urban area and immediate outflow, and is strongly correlated with CO indicating a strong urban source. The importance of nitrate decreases with distance from the city

  5. Fast airborne aerosol size and chemistry measurements with the high resolution aerosol mass spectrometer during the MILAGRO Campaign

    Science.gov (United States)

    Decarlo, P. F.; Dunlea, E. J.; Kimmel, J. R.; Aiken, A. C.; Sueper, D.; Crounse, J.; Wennberg, P. O.; Emmons, L.; Shinozuka, Y.; Clarke, A.; Zhou, J.; Tomlinson, J.; Collins, D. R.; Knapp, D.; Weinheimer, A. J.; Montzka, D. D.; Campos, T.; Jimenez, J. L.

    2007-12-01

    The concentration, size, and composition of non-refractory submicron aerosol (NR-PM1) was measured over Mexico City and central Mexico with a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) onboard the NSF/NCAR C-130 aircraft as part of the MILAGRO field campaign. This was the first aircraft deployment of the HR-ToF-AMS, in which the instrument performed very well, and provided 12 s data. The aerosol mass from the AMS correlates strongly with other aerosol measurements on board the aircraft. Organic aerosol (OA) species dominate the NR-PM1 mass. OA correlates strongly with CO and HCN indicating that pollution (mostly secondary OA, SOA) and biomass burning (BB) are the main OA sources. The OA to CO ratio indicates a typical value for aged air of around 80 μg m-3 (STP) ppm-1. This is within the range observed in outflow from the Northeastern US, which could be due to a compensating effect between higher BB but lower biogenic VOC emissions during this study. The O/C atomic ratio for OA is calculated from the HR mass spectra and shows a clear increase with photochemical age, as SOA forms rapidly and quickly overwhelms primary urban OA, consistent with Volkamer et al. (2006) and Kleinman et al. (2007b). BB OA is marked by signals at m/z 60 and 73, and also by a signal enhancement at large m/z indicative of larger molecules or more resistance to fragmentation. The main inorganic components show different spatial patterns and size distributions. Sulfate is regional in nature with clear volcanic and petrochemical/power plant sources, while the urban area is not a major source for this species. Nitrate is enhanced significantly in the urban area and immediate outflow, and is strongly correlated with CO indicating a strong urban source. The importance of nitrate decreases with distance from the city likely due to evaporation. BB does not appear to be a strong source of nitrate despite its high emissions of nitrogen oxides, presumably due to low ammonia

  6. Fast airborne aerosol size and chemistry measurements with the high resolution aerosol mass spectrometer during the MILAGRO Campaign

    Directory of Open Access Journals (Sweden)

    P. F. DeCarlo

    2007-12-01

    Full Text Available The concentration, size, and composition of non-refractory submicron aerosol (NR-PM1 was measured over Mexico City and central Mexico with a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS onboard the NSF/NCAR C-130 aircraft as part of the MILAGRO field campaign. This was the first aircraft deployment of the HR-ToF-AMS, in which the instrument performed very well, and provided 12 s data. The aerosol mass from the AMS correlates strongly with other aerosol measurements on board the aircraft. Organic aerosol (OA species dominate the NR-PM1 mass. OA correlates strongly with CO and HCN indicating that pollution (mostly secondary OA, SOA and biomass burning (BB are the main OA sources. The OA to CO ratio indicates a typical value for aged air of around 80 μg m−3 (STP ppm−1. This is within the range observed in outflow from the Northeastern US, which could be due to a compensating effect between higher BB but lower biogenic VOC emissions during this study. The O/C atomic ratio for OA is calculated from the HR mass spectra and shows a clear increase with photochemical age, as SOA forms rapidly and quickly overwhelms primary urban OA, consistent with Volkamer et al. (2006 and Kleinman et al. (2007b. BB OA is marked by signals at m/z 60 and 73, and also by a signal enhancement at large m/z indicative of larger molecules or more resistance to fragmentation. The main inorganic components show different spatial patterns and size distributions. Sulfate is regional in nature with clear volcanic and petrochemical/power plant sources, while the urban area is not a major source for this species. Nitrate is enhanced significantly in the urban area and immediate outflow, and is strongly correlated with CO indicating a strong urban source. The importance of nitrate decreases with distance from the city likely due to evaporation. BB does not appear to be a strong source of nitrate

  7. The role of method of production and resolution of the DEM on slope-units delineation for landslide susceptibility assessment - Ubaye Valley, French Alps case study

    Science.gov (United States)

    Schlögel, Romy; Marchesini, Ivan; Alvioli, Massimiliano; Reichenbach, Paola; Rossi, Mauro; Malet, Jean-Philippe

    2016-04-01

    Landslide susceptibility assessment forms the basis of any hazard mapping, which is one of the essential parts of quantitative risk mapping. For the same study area, different susceptibility maps can be achieved depending on the type of susceptibility mapping methods, mapping unit, and scale. In the Ubaye Valley (South French Alps), we investigate the effect of resolution and method of production of the DEM to delineate slope units for landslide susceptibility mapping method. Slope units delineation has been processed using multiple combinations of circular variance and minimum area size values, which are the input parameters for a new software for terrain partitioning. We rely on this method taking into account homogeneity of aspect direction inside each unit and inhomogeneity between different units. We computed slope units delineation for 5, 10 and 25 meters resolution DEM, and investigate statistical distributions of morphometric variables within the different polygons. Then, for each different slope units partitioning, we calibrated a landslide susceptibility model, considering landslide bodies and scarps as a dependent variable (binary response). This work aims to analyse the role of DEM resolution on slope-units delineation for landslide susceptibility assessment. Area Under the Curve of the Receiver Operating Characteristic is investigated for the susceptibility model calculations. In addition, we analysed further the performance of the Logistic Regression Model by looking at the percentage of significant variable in the statistical analyses. Results show that smaller slope units have a better chance of containing a smaller number of thematic and morphometric variables, allowing for an easier classification. Reliability of the models according to the DEM resolution considered as well as scarp area and landslides bodies presence/absence as dependent variable are discussed.

  8. High Resolution Mass Spectrometry of Seasonal Aerosol Samples From an Urban Location in the Italian Po Valley

    Science.gov (United States)

    Mahon, Brendan; Giorio, Chiara; Gallimore, Peter J.; Zielinski, Arthur T.; Tapparo, Andrea; Kalberer, Markus

    2016-04-01

    The Po Valley in Northern Italy represents one of the most polluted environments in Europe, with PM2.5 and ozone concentrations regularly exceeding 100μg/m3 and 50ppb respectively. Particularly during winter, prolonged inversion conditions together with biomass burning and anthropogenic emissions regularly lead to severe air pollution events. Over the course of several months in 2013-14, we carried out a sampling program at a city-centre site in Padova, Italy, collecting 24-hour high-volume aerosol filter samples, 18 in winter (mid December - mid March) and 20 in summer (late May - late July). Utilising high-resolution Orbitrap mass spectrometry techniques, we have characterised these sample sets to examine the long-term variation in aerosol composition over the sampling campaign and to determine the effect of anthropogenic gaseous pollutants such as NOx and SO2 on the composition of organic particle components. The results showed that between ca. 450-700 ions were measured in each sample in both the summer and winter sample sets, however the majority (90%) of ions in the winter samples were below 300m/z and below 380m/z in the summer samples. A much higher percentage of CHO-only ions were found in winter (ca. 27%) compared to the summer samples (ca. 6%), indicating a higher degree of photochemical reactions taking place involving pollutants such as NOx and SO2 in summer. Our results represent the first long term data set of high-resolution measurements of aerosol composition and demonstrate that this technique is an important tool in evaluating the composition of aerosol particles in complex polluted urban areas.

  9. The role of inflammation resolution speed in airway smooth muscle mass accumulation in asthma: insight from a theoretical model.

    Directory of Open Access Journals (Sweden)

    Igor L Chernyavsky

    Full Text Available Despite a large amount of in vitro data, the dynamics of airway smooth muscle (ASM mass increase in the airways of patients with asthma is not well understood. Here, we present a novel mathematical model that describes qualitatively the growth dynamics of ASM cells over short and long terms in the normal and inflammatory environments typically observed in asthma. The degree of ASM accumulation can be explained by an increase in the rate at which ASM cells switch between non-proliferative and proliferative states, driven by episodic inflammatory events. Our model explores the idea that remodelling due to ASM hyperplasia increases with the frequency and magnitude of these inflammatory events, relative to certain sensitivity thresholds. It highlights the importance of inflammation resolution speed by showing that when resolution is slow, even a series of small exacerbation events can result in significant remodelling, which persists after the inflammatory episodes. In addition, we demonstrate how the uncertainty in long-term outcome may be quantified and used to design an optimal low-risk individual anti-proliferative treatment strategy. The model shows that the rate of clearance of ASM proliferation and recruitment factors after an acute inflammatory event is a potentially important, and hitherto unrecognised, target for anti-remodelling therapy in asthma. It also suggests new ways of quantifying inflammation severity that could improve prediction of the extent of ASM accumulation. This ASM growth model should prove useful for designing new experiments or as a building block of more detailed multi-cellular tissue-level models.

  10. A new generation of high resolution mass analyzer to study organic and mineral matters simulating those of Titan and Enceladus: the Cosmorbitrap project

    Science.gov (United States)

    Selliez-Vandernotte, Laura; Briois, Christelle; Carrasco, Nathalie; Thirkell, Laurent; Cosmorbitrap Team

    2016-10-01

    Cassini mission highlighted for the first time, among many discoveries, the chemistry occurring in Titan atmosphere (with the detection of positive and negative ions at very high masses) and the presence of organic matter hidden in Enceladus plumes (1; 2). Can you imagine which results would have been obtained with a better resolution?Today, in lab, a new generation of high resolution mass analyzer called OrbitrapTM can reach a resolution of 106 at m/z=200 (3; 4). It gives a precise reading of the mass on charge, using a purely electric field and applying a Fourier transform. A project named Cosmorbitrap is trying to incorporate an OrbitrapTM analyzer, as a part of a mass spectrometer instrument, in order to propose it for a future mission toward the Saturn moons but also toward many other objects in the Solar System (5).Among the various tests required, we are optimizing the analysis of mineral and organic matter. This includes mass precision, resolution, isotopic detection, isotopic ratios and identification of unknown molecules. Starting with simple molecules, we will study more and more complex molecules and mixtures like Titan and Enceladus analogs. This meeting could be a great opportunity to explain our last results, to present benefits and limits of this instrument.(1) Waite et al, 2007, Science(2) Waite et al, 2009, Nature(3) Makarov, 2000(4) Denisov et al, 2012(5) Briois et al, 2016, Planetary and Space Science (in press)

  11. Ambient Observations of Organic Nitrogen Compounds in Submicrometer Aerosols in New York Using High Resolution Aerosol Mass Spectrometry

    Science.gov (United States)

    Zhou, S.; Ge, X.; Xu, J.; Sun, Y.; Zhang, Q.

    2015-12-01

    Organic nitrogen (ON) compounds, which include amines, nitriles, organic nitrates, amides, and N-containing aromatic heterocycles, are an important class of compounds ubiquitously detected in atmospheric particles and fog and cloud droplets. Previous studies indicate that these compounds can make up a significant fraction (20-80%) of the total nitrogen (N) content in atmospheric condensed phases and play important roles in new particle formation and growth and affecting the optical and hygroscopicity of aerosols. In this study, we report the observation of ON compounds in submicrometer particles (PM1) at two locations in New York based on measurements using Aerodyne high-resolution time-of-flight mass spectrometer (HR-ToF-AMS). One study was conducted as part of the US Department of Energy funded Aerosol Lifecyle - Intensive Operation Period (ALC-IOP) campaign at Brookhaven National Lab (BNL, 40.871˚N, 72.89˚W) in summer, 2011 and the other was conducted at the Queen's College (QC) in New York City (NYC) in summer, 2009. We observed a notable amount of N-containing organic fragment ions, CxHyNp+ and CxHyOzNp+, in the AMS spectra of organic aerosols at both locations and found that they were mainly associated with amino functional groups. Compared with results from lab experiments, the C3H8N+ at m/z = 58 was primarily attributed to trimethylamine. In addition, a significant amount of organonitrates was observed at BNL. Positive matrix factorization (PMF) analysis of the high resolution mass spectra (HRMS) of organic aerosols identified a unique nitrogen-enriched OA (NOA) factor with elevated nitrogen-to-carbon (N/C) at both BNL and QC. Analysis of the size distributions, volatility profiles, and correlations with external tracer indicates that acid-base reactions of amino compounds with sulfate and acidic gas were mainly responsible for the formation of amine salts. Photochemical production was also observed to play a role in the formation of NOA. Bivariate polar

  12. Teaching Mass Transfer and Filtration Using Crossflow Reverse Osmosis and Nanofiltration: An Experiment for the Undergraduate Unit Operations Lab

    Science.gov (United States)

    Anastasio, Daniel; McCutcheon, Jeffrey

    2012-01-01

    A crossflow reverse osmosis (RO) system was built for a senior-level chemical engineering unit operations laboratory course. Intended to teach students mass transfer fundamentals related to membrane separations, students tested several commercial desalination membranes, measuring water flux and salt rejections at various pressures, flow rates, and…

  13. Teaching Mass Transfer and Filtration Using Crossflow Reverse Osmosis and Nanofiltration: An Experiment for the Undergraduate Unit Operations Lab

    Science.gov (United States)

    Anastasio, Daniel; McCutcheon, Jeffrey

    2012-01-01

    A crossflow reverse osmosis (RO) system was built for a senior-level chemical engineering unit operations laboratory course. Intended to teach students mass transfer fundamentals related to membrane separations, students tested several commercial desalination membranes, measuring water flux and salt rejections at various pressures, flow rates, and…

  14. A new method to discriminate secondary organic aerosols from different sources using high-resolution aerosol mass spectra

    Directory of Open Access Journals (Sweden)

    M. F. Heringa

    2012-02-01

    Full Text Available Organic aerosol (OA represents a significant and often major fraction of the non-refractory PM1 (particulate matter with an aerodynamic diameter da < 1 μm mass. Secondary organic aerosol (SOA is an important contributor to the OA and can be formed from biogenic and anthropogenic precursors. Here we present results from the characterization of SOA produced from the emissions of three different anthropogenic sources. SOA from a log wood burner, a Euro 2 diesel car and a two-stroke Euro 2 scooter were characterized with an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS and compared to SOA from α-pinene.

    The emissions were sampled from the chimney/tailpipe by a heated inlet system and filtered before injection into a smog chamber. The gas phase emissions were irradiated by xenon arc lamps to initiate photo-chemistry which led to nucleation and subsequent particle growth by SOA production.

    Duplicate experiments were performed for each SOA type, with the averaged organic mass spectra showing Pearson's r values >0.94 for the correlations between the four different SOA types after five hours of aging. High-resolution mass spectra (HR-MS showed that the dominant peaks in the MS, m/z 43 and 44, are dominated by the oxygenated ions C2H3O+ and CO2+, respectively, similarly to the relatively fresh semi-volatile oxygenated OA (SV-OOA observed in the ambient aerosol. The atomic O:C ratios were found to be in the range of 0.25–0.55 with no major increase during the first five hours of aging. On average, the diesel SOA showed the lowest O:C ratio followed by SOA from wood burning, α-pinene and the scooter emissions. Grouping the fragment ions revealed that the SOA source with the highest O:C ratio had the largest fraction of small ions.

    The HR data of the four sources could be clustered and separated using

  15. A new method to discriminate secondary organic aerosols from different sources using high-resolution aerosol mass spectra

    Directory of Open Access Journals (Sweden)

    M. F. Heringa

    2011-10-01

    Full Text Available Organic aerosol (OA represents a significant and often major fraction of the non-refractory PM1 (particulate matter with an aerodynamic diameter da < 1 μm mass. Secondary organic aerosol (SOA is an important contributor to the OA and can be formed from biogenic and anthropogenic precursors. Here we present results from the characterization of SOA produced from the emissions of three different anthropogenic sources. SOA from a log wood burner, a Euro 2 diesel car and a two-stroke Euro 2 scooter were characterized with an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS and compared to SOA from α-pinene.

    The emissions were sampled from the chimney/tailpipe by a heated inlet system and filtered before injection into a smog chamber. The gas phase emissions were irradiated by xenon arc lamps to initiate photo-chemistry which led to nucleation and subsequent particle growth by SOA production.

    Duplicate experiments were performed for each SOA type, with the averaged organic mass spectra in the m/z range 12–250 showing Pearson's r values >0.94 for the correlations between the different SOA types after 5 h of aging. High-resolution mass spectra (HR-MS showed that the dominant peaks in the MS, m/z 43 and 44, are dominated by the oxygenated ions C2H3O+ and CO2+, respectively, similarly to the relatively fresh semi-volatile oxidized OA (SV-OOA observed in the ambient aerosol. The atomic O : C ratios were found to be in the range of 0.25–0.55 with no major increase during the first 5 h of aging. On average, the diesel SOA showed the lowest O : C ratio followed by SOA from wood burning, α-pinene and the scooter emissions. Grouping the fragment ions based on their carbon number revealed that the SOA source with the highest O : C ratio had the largest fraction of small ions. Fragment ions

  16. Skin imprinting in silica plates: a potential diagnostic methodology for leprosy using high-resolution mass spectrometry.

    Science.gov (United States)

    Lima, Estela de Oliveira; de Macedo, Cristiana Santos; Esteves, Cibele Zanardi; de Oliveira, Diogo Noin; Pessolani, Maria Cristina Vidal; Nery, José Augusto da Costa; Sarno, Euzenir Nunes; Catharino, Rodrigo Ramos

    2015-04-07

    Leprosy is a chronic infectious disease caused by Mycobacterium leprae, which primarily infects macrophages and Schwann cells, affecting skin and peripheral nerves. Clinically, the most common form of identification is through the observation of anesthetic lesions on skin; however, up to 30% of infected patients may not present this clinical manifestation. Currently, the gold standard diagnostic test for leprosy is based on skin lesion biopsy, which is invasive and presents low sensibility for suspect cases. Therefore, the development of a fast, sensible and noninvasive method that identifies infected patients would be helpful for assertive diagnosis. The aim of this work was to identify lipid markers in leprosy patients directly from skin imprints, using a mass spectrometric analytical strategy. For skin imprint samples, a 1 cm(2) silica plate was gently pressed against the skin of patients or healthy volunteers. Imprinted silica lipids were extracted and submitted to direct-infusion electrospray ionization high-resolution mass spectrometry (ESI-HRMS). All samples were differentiated using a lipidomics-based data workup employing multivariate data analysis, which helped electing different lipid markers, for example, mycobacterial mycolic acids, inflammatory and apoptotic molecules were identified as leprosy patients' markers. Otherwise, phospholipids and gangliosides were pointed as healthy volunteers' skin lipid markers, according to normal skin composition. Results indicate that silica plate skin imprinting associated with ESI-HRMS is a promising fast and sensible leprosy diagnostic method. With a prompt leprosy diagnosis, an early and effective treatment could be feasible and thus the chain of leprosy transmission could be abbreviated.

  17. On-sky Doppler performance of TOU optical very high-resolution spectrograph for detecting low-mass planets

    Science.gov (United States)

    Ge, Jian; Ma, Bo; Sithajan, Sirinrat; Singer, Michael A.; Powell, Scott; Varosi, Frank; Zhao, Bo; Schofield, Sidney; Liu, Jian; Grieves, Nolan; Cassette, Anthony; Avner, Louis; Jakeman, Hali; Muterspaugh, Matthew; Williamson, Michael; Barnes, Rory

    2016-08-01

    The TOU robotic, compact very high resolution optical spectrograph (R=100,000, 0.38-0.9 microns) has been fully characterized at the 2 meter Automatic Spectroscopy Telescope (AST) at Fairborn Observatory in Arizona during its pilot survey of 12 bright FGK dwarfs in 2015. This instrument has delivered sub m/s Doppler precision for bright reference stars (e.g., 0.7 m/s for Tau Ceti over 60 days) with 5-30 min exposures and 0.7 m/s long-term instrument stability, which is the best performance among all of the known Doppler spectrographs to our knowledge. This performance was achieved by maintaining the instrument in a very high vacuum of 1 micron torr and about 0.5 mK (RMS) long-term temperature stability through an innovative close-loop instrument bench temperature control. It has discovered a 21 Earth-mass planet (P=43days) around a bright K dwarf and confirmed three super-Earth planetary systems, HD 1461, 190360 and HD 219314. This instrument will be used to conduct the Dharma Planet Survey (DPS) in 2016-2019 to monitor 100 nearby very bright FGK dwarfs (most of them brighter than V=8) at the dedicated 50-inch Robotic Telescope on Mt. Lemmon. With very high RV precision and high cadence ( 100 observations per target randomly spread over 450 days), a large number of rocky planets, including possible habitable ones, are expected to be detected. The survey also provides the largest single homogenous high precision RV sample of nearby stars for studying low mass planet populations and constraining various planet formation models. Instrument on-sky performance is summarized.

  18. Identification of Putative Steroid Receptor Antagonists in Bottled Water: Combining Bioassays and High-Resolution Mass Spectrometry

    Science.gov (United States)

    Wagner, Martin; Schlüsener, Michael P.; Ternes, Thomas A.; Oehlmann, Jörg

    2013-01-01

    Endocrine disrupting chemicals (EDCs) are man-made compounds interfering with hormone signaling and thereby adversely affecting human health. Recent reports provide evidence for the presence of EDCs in commercially available bottled water, including steroid receptor agonists and antagonists. However, since these findings are based on biological data the causative chemicals remain unidentified and, therefore, inaccessible for toxicological evaluation. Thus, the aim of this study is to assess the antiestrogenic and antiandrogenic activity of bottled water and to identify the causative steroid receptor antagonists. We evaluated the antiestrogenic and antiandrogenic activity of 18 bottled water products in reporter gene assays for human estrogen receptor alpha and androgen receptor. Using nontarget high-resolution mass spectrometry (LTQ-Orbitrap Velos), we acquired corresponding analytical data. We combined the biological and chemical information to determine the exact mass of the tentative steroid receptor antagonist. Further MSn experiments elucidated the molecule’s structure and enabled its identification. We detected significant antiestrogenicity in 13 of 18 products. 16 samples were antiandrogenic inhibiting the androgen receptor by up to 90%. Nontarget chemical analysis revealed that out of 24520 candidates present in bottled water one was consistently correlated with the antagonistic activity. By combining experimental and in silico MSn data we identified this compound as di(2-ethylhexyl) fumarate (DEHF). We confirmed the identity and biological activity of DEHF and additional isomers of dioctyl fumarate and maleate using authentic standards. Since DEHF is antiestrogenic but not antiandrogenic we conclude that additional, yet unidentified EDCs must contribute to the antagonistic effect of bottled water. Applying a novel approach to combine biological and chemical analysis this is the first study to identify so far unknown EDCs in bottled water. Notably

  19. Identification of putative steroid receptor antagonists in bottled water: combining bioassays and high-resolution mass spectrometry.

    Directory of Open Access Journals (Sweden)

    Martin Wagner

    Full Text Available Endocrine disrupting chemicals (EDCs are man-made compounds interfering with hormone signaling and thereby adversely affecting human health. Recent reports provide evidence for the presence of EDCs in commercially available bottled water, including steroid receptor agonists and antagonists. However, since these findings are based on biological data the causative chemicals remain unidentified and, therefore, inaccessible for toxicological evaluation. Thus, the aim of this study is to assess the antiestrogenic and antiandrogenic activity of bottled water and to identify the causative steroid receptor antagonists. We evaluated the antiestrogenic and antiandrogenic activity of 18 bottled water products in reporter gene assays for human estrogen receptor alpha and androgen receptor. Using nontarget high-resolution mass spectrometry (LTQ-Orbitrap Velos, we acquired corresponding analytical data. We combined the biological and chemical information to determine the exact mass of the tentative steroid receptor antagonist. Further MS(n experiments elucidated the molecule's structure and enabled its identification. We detected significant antiestrogenicity in 13 of 18 products. 16 samples were antiandrogenic inhibiting the androgen receptor by up to 90%. Nontarget chemical analysis revealed that out of 24520 candidates present in bottled water one was consistently correlated with the antagonistic activity. By combining experimental and in silico MS(n data we identified this compound as di(2-ethylhexyl fumarate (DEHF. We confirmed the identity and biological activity of DEHF and additional isomers of dioctyl fumarate and maleate using authentic standards. Since DEHF is antiestrogenic but not antiandrogenic we conclude that additional, yet unidentified EDCs must contribute to the antagonistic effect of bottled water. Applying a novel approach to combine biological and chemical analysis this is the first study to identify so far unknown EDCs in bottled water

  20. Hydrophilic interaction liquid chromatography coupled to high-resolution mass spectrometry to determine artificial sweeteners in environmental waters.

    Science.gov (United States)

    Salas, Daniela; Borrull, Francesc; Fontanals, Núria; Marcé, Rosa Maria

    2015-06-01

    Artificial sweeteners are food additives employed as sugar substitutes which are now considered to be emerging organic contaminants. In the present study, a method is developed for the determination of a group of artificial sweeteners in environmental waters. Considering the polar and hydrophilic character of these compounds, hydrophilic interaction liquid chromatography is proposed for their separation as an alternative to traditional reversed-phase liquid chromatography. Two stationary phases with different chemistry were compared for this purpose. For the detection of the analytes, high-resolution mass spectrometry (Orbitrap) was employed to take advantage of its benefits in terms of reliable quantification and confirmation for the measurement of accurate masses. Solid-phase extraction was chosen as the sample treatment, in which the extract in a mixture of NH4OH:MeOH:ACN (1:4:15) was directly injected into the chromatographic system, simplifying the analytical procedure. The optimized method was validated on river and waste water samples. For example, in the case of effluent water samples, limits of detection ranged from 0.002 to 0.7 μg/L and limits of quantification ranged from 0.004 to 1.5 μg/L. Apparent (whole method) recoveries ranged from 57 to 74% with intra-day precision (%RSD, n = 5) ranging from 6 to 25%. The method was successfully applied to water samples from different rivers in Catalonia and different waste water treatment plants in Tarragona. Acesulfame, cyclamate, saccharine and sucralose were found in several samples.

  1. Influence of heteroatom pre-selection on the molecular formula assignment of soil organic matter components determined by ultrahigh resolution mass spectrometry.

    Science.gov (United States)

    Ohno, Tsutomu; Ohno, Paul E

    2013-04-01

    Soil organic matter (SOM) is involved in many important ecosystem processes. Ultrahigh resolution mass spectrometry has become a powerful technique in the chemical characterization of SOM, allowing assignment of elemental formulae for thousands of peaks resolved in a typical mass spectrum. We investigated how the addition of N, S, and P heteroatoms in the formula calculation stage of the mass spectra processing workflow affected the formula assignments of mass spectra peaks. Dissolved organic matter extracted from plant biomass and soil as well as the soil humic acid fraction was studied. We show that the addition of S and P into the molecular formula calculation increased peak assignments on average by 17.3 % and 10.7 %, respectively, over the assignments based on the CHON elements frequently reported by SOM researchers using ultrahigh resolution mass spectrometry. The organic matter chemical characteristics as represented by van Krevelen diagrams were appreciably affected by differences in the heteroatom pre-selection for the three organic matter samples investigated, especially so for the wheat-derived dissolved organic matter. These results show that inclusion of both S and P heteroatoms into the formula calculation step, which is not routinely done, is important to obtain a more chemically complete interpretation of the ultrahigh resolution mass spectra of SOM.

  2. Sympathy for the Devil: Detailing the Effects of Planning-Unit Size, Thematic Resolution of Reef Classes, and Socioeconomic Costs on Spatial Priorities for Marine Conservation.

    Science.gov (United States)

    Cheok, Jessica; Pressey, Robert L; Weeks, Rebecca; Andréfouët, Serge; Moloney, James

    2016-01-01

    Spatial data characteristics have the potential to influence various aspects of prioritising biodiversity areas for systematic conservation planning. There has been some exploration of the combined effects of size of planning units and level of classification of physical environments on the pattern and extent of priority areas. However, these data characteristics have yet to be explicitly investigated in terms of their interaction with different socioeconomic cost data during the spatial prioritisation process. We quantify the individual and interacting effects of three factors-planning-unit size, thematic resolution of reef classes, and spatial variability of socioeconomic costs-on spatial priorities for marine conservation, in typical marine planning exercises that use reef classification maps as a proxy for biodiversity. We assess these factors by creating 20 unique prioritisation scenarios involving combinations of different levels of each factor. Because output data from these scenarios are analogous to ecological data, we applied ecological statistics to determine spatial similarities between reserve designs. All three factors influenced prioritisations to different extents, with cost variability having the largest influence, followed by planning-unit size and thematic resolution of reef classes. The effect of thematic resolution on spatial design depended on the variability of cost data used. In terms of incidental representation of conservation objectives derived from finer-resolution data, scenarios prioritised with uniform cost outperformed those prioritised with variable cost. Following our analyses, we make recommendations to help maximise the spatial and cost efficiency and potential effectiveness of future marine conservation plans in similar planning scenarios. We recommend that planners: employ the smallest planning-unit size practical; invest in data at the highest possible resolution; and, when planning across regional extents with the intention

  3. Very High Resolution 2.5km Surface Mass balance Modelling Forced with Non-Hydrostatic HARMONIE-AROME

    Science.gov (United States)

    Mottram, Ruth; Langen, Peter; Pagh Nielsen, Kristian; Yang, Xiaohua; Gleeson, Emily

    2017-04-01

    The numerical weather prediction (NWP) model system HARMONIE, developed in collaboration between 26 European and Mediterranean countries by the ALADIN-HIRLAM consortium, offers an opportunity for extraordinarily high resolution surface mass balance (SMB) modelling. We present some initial experimental simulations where HARMONIE-AROME output from the DMI's operational NWP system, is used to force an offline SMB model for the whole of Greenland. The output from HARMONIE-AROME is compared with automatic weather station data from the PROMICE network on the ice sheet to evaluate its performance. We find the HARMONIE-AROME to represents the surface weather over the ice sheet very well, in particular 2m temperature, surface temperature and wind speeds are well reproduced. Ongoing work to assess precipitation is complicated by the difficulties of measuring solid precipitation in Greenland. The SURFEX model provides the surface scheme for HARMONIE-AROME and output from this part of the model is compared with that from the offline SMB model to assess the comparability of HARMONIE-AROME with the HIRHAM5 regional climate model. Improved SMB modelling is crucial in Greenland and Iceland not just to assess the rate of glacier change and sea level rise but also to facilitate infrastructural considerations such as communal water supplies, hydropower development and mineral extraction. The model evaluation here suggests that HARMONIE may be helpful in existing NWP domains that cover for example the Svalbard archipelago, the Alps and the Scandinavian mountain glaciers, in order to assess glacier runoff and change.

  4. Localization of iron in rice grain using synchrotron X-ray fluorescence microscopy and high resolution secondary ion mass spectrometry

    KAUST Repository

    Kyriacou, Bianca

    2014-03-01

    Cereal crops accumulate low levels of iron (Fe) of which only a small fraction (5-10%) is bioavailable in human diets. Extensive co-localization of Fe in outer grain tissues with phytic acid, a strong chelator of metal ions, results in the formation of insoluble complexes that cannot be digested by humans. Here we describe the use of synchrotron X-ray fluorescence microscopy (XFM) and high resolution secondary ion mass spectrometry (NanoSIMS) to map the distribution of Fe, zinc (Zn), phosphorus (P) and other elements in the aleurone and subaleurone layers of mature grain from wild-type and an Fe-enriched line of rice (Oryza sativa L.). The results obtained from both XFM and NanoSIMS indicated that most Fe was co-localized with P (indicative of phytic acid) in the aleurone layer but that a small amount of Fe, often present as "hotspots", extended further into the subaleurone and outer endosperm in a pattern that was not co-localized with P. We hypothesize that Fe in subaleurone and outer endosperm layers of rice grain could be bound to low molecular weight chelators such as nicotianamine and/or deoxymugineic acid. © 2014.

  5. Molecular-level evidence provided by ultrahigh resolution mass spectrometry for oil-derived doc in groundwater at Bemidji, Minnesota.

    Science.gov (United States)

    Islam, Ananna; Ahmed, Arif; Hur, Manhoi; Thorn, Kevin; Kim, Sunghwan

    2016-12-15

    Dissolved organic matter samples extracted from ground water at the USGS Bemidji oil spill site in Minnesota were investigated by ultrahigh resolution mass spectrometry. Principle component analysis (PCA) of the elemental composition assignments of the samples showed that the score plots for the contaminated sites were well separated from those for the uncontaminated sites. Additionally, spectra obtained from the same sampling site 7 and 19 years after the spill were grouped together in the score plot, strongly suggesting a steady state of contamination within the 12year interval. The double bond equivalence (DBE) of Ox class compounds was broader for the samples from the contaminated sites, because of the complex nature of oil and the consequent formation of compounds with saturated and/or aromatic structures from the oxygenated products of oil. In addition, Ox class compounds with a relatively smaller number of x (x<8; x=number of oxygen) and OxS1 class compounds were more abundant in the samples from the contaminated sites, because of the lower oxygen and higher sulfur contents of the oil compared to humic substances. The molecular-level signatures presented here can be a fundamental basis for in-depth analysis of oil contamination. Copyright © 2016 Elsevier B.V. All rights reserved.

  6. Comprehensive Characterization of Glycosylation and Hydroxylation of Basement Membrane Collagen IV by High-Resolution Mass Spectrometry.

    Science.gov (United States)

    Basak, Trayambak; Vega-Montoto, Lorenzo; Zimmerman, Lisa J; Tabb, David L; Hudson, Billy G; Vanacore, Roberto M

    2016-01-04

    Collagen IV is the main structural protein that provides a scaffold for assembly of basement membrane proteins. Posttranslational modifications such as hydroxylation of proline and lysine and glycosylation of lysine are essential for the functioning of collagen IV triple-helical molecules. These modifications are highly abundant posing a difficult challenge for in-depth characterization of collagen IV using conventional proteomics approaches. Herein, we implemented an integrated pipeline combining high-resolution mass spectrometry with different fragmentation techniques and an optimized bioinformatics workflow to study posttranslational modifications in mouse collagen IV. We achieved 82% sequence coverage for the α1 chain, mapping 39 glycosylated hydroxylysine, 148 4-hydroxyproline, and seven 3-hydroxyproline residues. Further, we employed our pipeline to map the modifications on human collagen IV and achieved 85% sequence coverage for the α1 chain, mapping 35 glycosylated hydroxylysine, 163 4-hydroxyproline, and 14 3-hydroxyproline residues. Although lysine glycosylation heterogeneity was observed in both mouse and human, 21 conserved sites were identified. Likewise, five 3-hydroxyproline residues were conserved between mouse and human, suggesting that these modification sites are important for collagen IV function. Collectively, these are the first comprehensive maps of hydroxylation and glycosylation sites in collagen IV, which lay the foundation for dissecting the key role of these modifications in health and disease.

  7. [Characterization of pyrolysis of waste printed circuit boards by high-resolution pyrolysis gas chromatography-mass spectrometry].

    Science.gov (United States)

    Zhang, Yanhong; Huang, Hong; Xia, Zhengbin; Chen, Huanqin

    2008-07-01

    Thermal degradation of pyrolysis of waste circuit boards was investigated by high-resolution pyrolysis gas chromatography-mass spectrometry (PyGC-MS) and thermogravimetry (TG). In helium atmosphere, the products of FR-4 waste printed circuit board were pyrolyzed at 350, 450, 550, 650, and 750 degrees degrees C, separately, and the pyrolysis products were identified by online MS. The results indicated that the pyrolysis products of the FR-4 waste circuit board were three kinds of substances, such as the low boiling point products, phenol, bisphenol and their related products. Moreover, under 300 degrees degrees C, only observed less pyrolysis products. As the increase of pyrolysis temperature, the relative content of the low boiling point products increased. In the range of 450-650 degrees degrees C, the qualitative analysis and character were similar, and the relative contents of phenol and bisphenol were higher. The influence of pyrolysis temperature on pyrolyzate yields was studied. On the basis of the pyrolyzate profile and the dependence of pyrolyzate yields on pyrolysis temperature, the thermal degradation mechanism of brominated epoxy resin was proposed.

  8. Tracing nitrogenous disinfection byproducts after medium pressure UV water treatment by stable isotope labeling and high resolution mass spectrometry.

    Science.gov (United States)

    Kolkman, Annemieke; Martijn, Bram J; Vughs, Dennis; Baken, Kirsten A; van Wezel, Annemarie P

    2015-04-07

    Advanced oxidation processes are important barriers for organic micropollutants (e.g., pharmaceuticals, pesticides) in (drinking) water treatment. Studies indicate that medium pressure (MP) UV/H2O2 treatment leads to a positive response in Ames mutagenicity tests, which is then removed after granulated activated carbon (GAC) filtration. The formed potentially mutagenic substances were hitherto not identified and may result from the reaction of photolysis products of nitrate with (photolysis products of) natural organic material (NOM). In this study we present an innovative approach to trace the formation of disinfection byproducts (DBPs) of MP UV water treatment, based on stable isotope labeled nitrate combined with high resolution mass spectrometry. It was shown that after MP UV treatment of artificial water containing NOM and nitrate, multiple nitrogen containing substances were formed. In total 84 N-DBPs were detected at individual concentrations between 1 to 135 ng/L bentazon-d6 equivalents, with a summed concentration of 1.2 μg/L bentazon-d6 equivalents. The chemical structures of three byproducts were confirmed. Screening for the 84 N-DBPs in water samples from a full-scale drinking water treatment plant based on MP UV/H2O2 treatment showed that 22 of the N-DBPs found in artificial water were also detected in real water samples.

  9. Application of Holistic Liquid Chromatography-High Resolution Mass Spectrometry Based Urinary Metabolomics for Prostate Cancer Detection and Biomarker Discovery.

    Directory of Open Access Journals (Sweden)

    Tong Zhang

    Full Text Available Human exhibit wide variations in their metabolic profiles because of differences in genetic factors, diet and lifestyle. Therefore in order to detect metabolic differences between individuals robust analytical methods are required. A protocol was produced based on the use of Liquid Chromatography- High Resolution Mass Spectrometry (LC-HRMS in combination with orthogonal Hydrophilic Interaction (HILIC and Reversed Phase (RP liquid chromatography methods for the analysis of the urinary metabolome, which was then evaluated as a diagnostic tool for prostate cancer (a common but highly heterogeneous condition. The LC-HRMS method was found to be robust and exhibited excellent repeatability for retention times (0.9. In addition, using the receiver operator characteristics (ROC test, the area under curve (AUC for the combination of the four best characterised biomarker compounds was 0.896. The four biomarker compounds were also found to differ significantly (P<0.05 between an independent patient cohort and controls. This is the first time such a rigorous test has been applied to this type of model. If validated, the established protocol provides a robust approach with a potentially wide application to metabolite profiling of human biofluids in health and disease.

  10. Physical Properties of Young Brown Dwarfs and Very Low-Mass Stars Inferred from High-Resolution Model Spectra

    CERN Document Server

    Rice, Emily L; McLean, Ian S; Prato, L; Kirkpatrick, J Davy

    2009-01-01

    By comparing near-infrared spectra with atmosphere models, we infer the effective temperature, surface gravity, projected rotational velocity, and radial velocity for 21 very-low-mass stars and brown dwarfs. The unique sample consists of two sequences in spectral type from M6-M9, one of 5-10 Myr objects and one of >1 Gyr field objects. A third sequence is comprised of only ~M6 objects with ages ranging from 1 Gyr. Spectra were obtained in the J band at medium (R~2,000) and high (R~20,000) resolutions with NIRSPEC on the Keck II telescope. Synthetic spectra were generated from atmospheric structures calculated with the PHOENIX model atmosphere code. Using multi-dimensional least-squares fitting and Monte Carlo routines we determine the best-fit model parameters for each observed spectrum and note which spectral regions provide consistent results. We identify successes in the reproduction of observed features by atmospheric models, including pressure-broadened KI lines, and investigate deficiencies in the model...

  11. Genetic engineering, high resolution mass spectrometry and nuclear magnetic resonance spectroscopy elucidate the bikaverin biosynthetic pathway in Fusarium fujikuroi.

    Science.gov (United States)

    Arndt, Birgit; Studt, Lena; Wiemann, Philipp; Osmanov, Helena; Kleigrewe, Karin; Köhler, Jens; Krug, Isabel; Tudzynski, Bettina; Humpf, Hans-Ulrich

    2015-11-01

    Secondary metabolites of filamentous fungi can be highly bioactive, ranging from antibiotic to cancerogenic properties. In this study we were able to identify a new, yet unknown metabolite produced by Fusarium fujikuroi, an ascomycetous rice pathogen. With the help of genomic engineering and high-performance liquid chromatography (HPLC) coupled to high resolution mass spectrometry (HRMS) followed by isolation and detailed structure elucidation, the new substance could be designated as an unknown bikaverin precursor, missing two methyl- and one hydroxy group, hence named oxo-pre-bikaverin. Though the bikaverin gene cluster has been extensively studied in the past, elucidation of the biosynthetic pathway remained elusive due to a negative feedback loop that regulates the genes within the cluster. To decipher the bikaverin biosynthetic pathway and to overcome these negative regulation circuits, the structural cluster genes BIK2 and BIK3 were overexpressed independently in the ΔΔBIK2/BIK3+OE::BIK1 mutant background by using strong constitutive promoters. Using the software tool MZmine 2, the metabolite profile of the generated mutants obtained by HPLC-HRMS was compared, revealing further intermediates.

  12. Comprehensive characterization and identification of antioxidants in Folium Artemisiae Argyi using high-resolution tandem mass spectrometry.

    Science.gov (United States)

    Han, Binsong; Xin, Zhongquan; Ma, Shasha; Liu, Wenbin; Zhang, Bingyang; Ran, Lu; Yi, Lunzhao; Ren, Dabing

    2017-09-15

    Antioxidants from natural sources, such as vegetables and fruits, are attracting more and more interest. In this work, we evaluated the antioxidant potential of Folium Artemisia Argyi, a traditional Chinese herb medicine and food supplement. The total phenolic content, total flavonoid content, and antioxidant ability of the crude extracts and fractions obtained from consecutively partition of n-hexane, ethyl acetate, and n-butanol were measured and compared. Ethyl acetate fraction shows the highest total phenolic and flavonoid contents and highest antioxidant capability with regard to DPPH, ABTS, superoxide anion free radical scavenging ability, and ferric-reducing antioxidant power. In addition, the potential antioxidant components were screened by DPPH-UHPLC-MS experiments and subsequently characterized by using high-resolution tandem mass spectrometry. This work finally identified 45 antioxidants, including organic acids, phenolic compounds, flavonoids, and methoxylated flavonoids. The results suggested that Folium Artemisiae Argyi is a potential inexpensive resource of natural antioxidants. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. Multi-detection of corticosteroids in sports doping and veterinary control using high-resolution liquid chromatography/time-of-flight mass spectrometry

    NARCIS (Netherlands)

    Touber, M.E.; Engelen, M.C.; Georgakopoulus, C.; Rhijn, van J.A.; Nielen, M.W.F.

    2007-01-01

    A liquid chromatography/time-of-flight mass spectrometry (LC/TOFMS) method was developed using the latest high-resolution LC column technology, the ultra performance liquid chromatography (UPLC (TM)), and electrospray ionization (ESI) in the positive ion mode. Gradient UPLC separation conditions wer

  14. Qualitative aspects and validation of a screening method for pesticides in vegetables and fruits based on liquid chromatography coupled to full scan high resolution (Orbitrap) mass spectrometry

    NARCIS (Netherlands)

    Mol, J.G.J.; Zomer, P.; Koning, de A.

    2012-01-01

    The analytical capabilities of liquid chromatography with single-stage high-resolution mass spectrometry have been investigated with emphasis on qualitative aspects related to selective detection during screening and to identification. The study involved 21 different vegetable and fruit commodities,

  15. High-resolution line-scan analysis of resin-embedded sediments using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS)

    NARCIS (Netherlands)

    Hennekam, Rick|info:eu-repo/dai/nl/357286081; Jilbert, Tom|info:eu-repo/dai/nl/304835714; Mason, Paul R D|info:eu-repo/dai/nl/304829331; de Lange, Gert J.|info:eu-repo/dai/nl/073930962; Reichart, Gert Jan|info:eu-repo/dai/nl/165599081

    2015-01-01

    Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) line-scanning is a promising technique for producing high-resolution (μm-scale) geochemical records on resin-embedded sediments. However, this approach has not yet been thoroughly tested on sediment samples of known elemental

  16. High-resolution line-scan analysis of resin-embedded sediments using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS)

    NARCIS (Netherlands)

    Hennekam, R.; Jilbert, T.; de Lange, G.J.; Reichart, G.J.

    2015-01-01

    Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) line-scanning is a promising technique for producing high-resolution (µm-scale) geochemical records on resin-embedded sediments. However, this approach has not yet been thoroughly tested on sediment samples of known elemental

  17. The stellar mass-size relation for cluster galaxies at z = 1 with high angular resolution from the Gemini/GeMS multiconjugate adaptive optics system

    Science.gov (United States)

    Sweet, Sarah M.; Sharp, Robert; Glazebrook, Karl; Rigaut, Francois; Carrasco, Eleazar R.; Brodwin, Mark; Bayliss, Matthew; Stalder, Brian; Abraham, Roberto; McGregor, Peter

    2017-01-01

    We present the stellar mass-size relation for 49 galaxies within the z = 1.067 cluster SPT-CL J0546-5345, with full width at half-maximum ˜80-120 mas Ks-band data from the Gemini multiconjugate adaptive optics system (GeMS/GSAOI). This is the first such measurement in a cluster environment, performed at sub-kpc resolution at rest-frame wavelengths dominated by the light of the underlying old stellar populations. The observed stellar mass-size relation is offset from the local relation by 0.21 dex, corresponding to a size evolution proportional to (1 + z)-1.25, consistent with the literature. The slope of the stellar mass-size relation β = 0.74 ± 0.06, consistent with the local relation. The absence of slope evolution indicates that the amount of size growth is constant with stellar mass. This suggests that galaxies in massive clusters such as SPT-CL J0546-5345 grow via processes that increase the size without significant morphological interference, such as minor mergers and/or adiabatic expansion. The slope of the cluster stellar mass-size relation is significantly shallower if measured in Hubble Space Telescope (HST)/Advanced Camera for Surveys imaging at wavelengths blueward of the Balmer break, similar to rest-frame ultraviolet relations at z = 1 in the literature. The stellar mass-size relation must be measured at redder wavelengths, which are more sensitive to the old stellar population that dominates the stellar mass of the galaxies. The slope is unchanged when GeMS Ks-band imaging is degraded to the resolution of K-band HST/Near Infrared Camera and Multi-Object Spectrometer resolution but dramatically affected when degraded to Ks-band Magellan/FourStar resolution. Such measurements must be made with adaptive optics in order to accurately characterize the sizes of compact, z = 1 galaxies.

  18. Universal electromagnetic suspension balance with nanogramme mass resolution for measurement of sorption on small samples in top and bottom loading configurations

    Science.gov (United States)

    Norton, C. G.; Petermann, M.; Fieback, T. M.

    2017-04-01

    Determination of mass increase or decrease of very small amplitude is a task which goes hand in hand with gravimetric adsorption and absorption measurement and thermogravimetry. Samples are subjected to various process conditions and as such can experience a change in mass, i.e. when adsorbing gas from the process atmosphere, or can decrease in mass, such as when being dried or when thermal decomposition takes place. Current instruments used for such analysis, especially at high pressures, are often based on magnetic suspension balances, and have a maximum mass resolution of a few 10‑6 g. This necessitates more often than not quite significant sample quantities, which can sometimes not easily be manufactured, e.g. in the case of metal organic framework adsorbents, or which in other cases do not have a sufficient specific surface area resulting in low measuring effect. A new apparatus based on a high resolution thermogravimetric analyser has been developed. This new apparatus combines very high resolution of up to a few 10‑8 g with a relatively high sample mass of up to 1.5 g, whilst eliminating many of the disadvantages of the microbalances previously used in magnetic suspension balances. An interface was developed which permits free configuration of the new balance as top or bottom loading. Validation measurements of known adsorbents were subsequently performed, with sample quantities up to a factor of 174 smaller than in literature.

  19. High molecular weight SOA formation during limonene ozonolysis: insights from ultrahigh-resolution FT-ICR mass spectrometry characterization

    Directory of Open Access Journals (Sweden)

    S. Kundu

    2012-06-01

    Full Text Available The detailed molecular composition of laboratory generated limonene ozonolysis secondary organic aerosol (SOA was studied using ultrahigh-resolution Fourier transform ion cyclotron resonance (FT-ICR mass spectrometry. Approximately 1200 molecular formulas were identified in the SOA over the mass range of 140 to 850 Da. Four characteristic groups of high relative abundance species were observed; they indicate an array of accretion products that retain a large fraction of the limonene skeleton. The identified molecular formulas of each of the groups are related to one another by CH2, O and CH2O homologous series. The CH2 and O homologous series of the low molecular weight (MW SOA (m/z < 300 are explained with a combination of functionalization and fragmentation of radical intermediates and reactive uptake of gas-phase carbonyls. They include isomerization and elimination reactions of Criegee radicals, reactions between alkyl peroxy radicals, and scission of alkoxy radicals resulting from the Criegee radicals. The presence of compounds with 10–15 carbon atoms in the first group (e.g. C11H18O6 provides evidence for SOA formation by the reactive uptake of gas-phase carbonyls during limonene ozonolysis. The high MW compounds (m/z > 300 were found to constitute a significant number fraction of the identified SOA components. The formation of high MW compounds was evaluated by molecular formula trends, fragmentation analysis of select high MW compounds and a comprehensive reaction matrix including the identified low MW SOA, hydroperoxides and Criegee radicals as building blocks. Although the formation of high MW SOA may occur via a variety of radical and non-radical reaction channels, the combined approach indicates a greater importance of the non-condensation reactions over aldol and ester condensation reaction channels. Among these hemi-acetal reactions appear to be most

  20. Molecular composition of rainwater and aerosol during rain events in León, Spain, using high resolution mass spectrometry.

    Science.gov (United States)

    Fee, Anna

    2017-04-01

    Anna Fee (1), Markus Kalberer (1), Roberto Fraile (2), Amaya Castro (2), Ana. I. Calvo (2), Carlos Blanco-Alegre (2), Fernanda Oduber (2) and Mário Cerqueira (3). 1 Department of Chemistry, University of Cambridge, UK. 2 Department of Applied Chemistry and Physics, IMARENAB, University of León, Spain. 3 Department of Environmental Planning, University of Aveiro, Portugal. A wide range of atmospheric compounds which are present in rainwater are often also present in aerosol. They can be taken up during cloud droplet formation (in-cloud scavenging) or washed out during precipitation (below-cloud scavenging). Such compounds including aromatic hydrocarbons and organic nitrogen containing compounds are hazardous to health. In this study, the organic chemical composition of rainwater and aerosol from rain events in León, Spain, is being analysed using high resolution mass spectrometry. Collected rainwater along with high volume and low volume filters from rain events which occurred during spring, summer and winter of 2016 have been selected for analysis. Rainwater samples were prepared using Polymeric Reversed Phase Solid Phase Extraction (SPE) and filters have been extracted in water with and without SPE. Three different SPE polymer based sorbents were tested; one for extracting neutral compounds and two which are more suitable for extracting organic compounds containing sulphate and other polar functional groups. The sorbent for extracting neutral compounds was found to yield a higher number of compounds from the sample extraction than the other two varieties. Kendrick masses, Van Krevelen plots and carbon oxidation states have been investigated to identify compounds and patterns. Preliminary results show a predominance in peaks with O/C ratios between 0.2 and 0.7 and H/C ratios between 1 and 2 in both rain and aerosol samples which indicates substituted aromatic compounds. Cellulose material and fatty acids may also be present. The rain samples also have a

  1. Characterization of Organic Nitrate Formation in Limonene Secondary Organic Aerosol using High-Resolution Chemical Ionization Mass Spectrometry

    Science.gov (United States)

    Faxon, Cameron; Hammes, Julia; Peng, Jianfei; Hallquist, Mattias; Pathak, Ravi

    2016-04-01

    Previous work has shown that organic nitrates (RONO2) are prevalent in the boundary layer, and can contribute significantly to secondary organic aerosol formation. Monoterpenes, including limonene, have been shown to be precursors for the formation of these organic nitrates. Limonene has two double bonds, either of which may be oxidized by NO3 or O3. This leads to the generation of products that can subsequently condense or partition into the particle phase, producing secondary organic aerosol. In order to further elucidate the particle and gas phase product distribution of organic nitrates forming from the reactions of limonene and the nitrate radical (NO3), a series of experiments were performed in the Gothenburg Flow Reactor for Oxidation Studies at Low Temperatures (G-FROST), described by previous work. N2O5 was used as the source for NO3 and NO2, and a characterized diffusion source was used to introduce limonene into the flow reactor. All experiments were conducted in the absence of light, and the concentration of limonene was increased step-wise throughout each experiment to modify the ratio of N2O5to limonene. The experiments were conducted such that both limonene- and N2O5-limited regimes were present. Gas and particle phase products were measured using an iodide High-Resolution Time-of-Flight Mass Spectrometer (HR-ToF-CIMS) coupled to a Filter Inlet for Gases and AEROsols (FIGAERO, and particle size and SOA mass concentrations were derived using a Scanning Mobility Particle Sizer (SMPS). CIMS measurement techniques have previously been employed for the measurement of organic nitrate products of such compounds using multiple reagent ions. The use of this instrumentation allowed for the identification of chemical formulas for gas and particle phase species. The findings from the experiments will be presented in terms of the relative gas-particle partitioning of major products and the effects of N2O5/limonene ratios on product distributions. Additionally, a

  2. Molecular composition of biogenic secondary organic aerosols using ultrahigh resolution mass spectrometry: linking laboratory and field studies

    Science.gov (United States)

    Kourtchev, Ivan; Fuller, Stephen; Aalto, Juho; Healy, Robert; Alfara, Rami; Ruuskanen, Taina; Wenger, John; McFiggans, Gordon; Kulmala, Markku; Kalberer, Markus

    2013-04-01

    Biogenic volatile organic compounds (BVOCs) play an important role in atmospheric chemistry and give rise to secondary organic aerosols (SOA), which have effects on climate and human health. Laboratory chamber experiments have been performed during several decades in an attempt to mimic atmospheric SOA formation. However, it is still unclear how close the aerosol particles generated in laboratory experiments resemble atmospheric SOA with respect to their detailed chemical composition. To date, most laboratory experiments have been performed using a single organic precursor (e.g., alpha- or beta-pinene, isoprene) while in the atmosphere a wide range of precursors contribute to SOA, which results most likely in a more complex SOA composition compared to the one-precursor laboratory systems. The objective of this work is to compare laboratory generated SOA from oxidation of BVOCs mixtures and remote ambient samples using ultrahigh-resolution mass spectrometry (UHR-MS) that allows detection of hundreds of individual SOA constituents. We examined aerosol samples from a boreal forest site, Hyytiälä, Finland and determined that a dominant fraction of the detected compounds are reaction products of a multi-component mixture of BVOCs. In the subsequent smog chamber experiments, SOA was generated from the ozonolysis and OH initiated reactions with BVOC mixtures containing species (alpha- and beta-pinene, delta-3-carene, and isoprene) that are most abundant in Hyytiälä's environment. The laboratory experiments were performed at conditions (e.g., RH, aerosol seed, and VOC ratios) that would resemble those at the boreal sampling site during the summer period. The elemental composition of the complex mixtures from laboratory generated SOA samples were compared with field samples using statistical data analysis methods.

  3. Direct determination of acrylamide in food by gas chromatography-high-resolution time-of-flight mass spectrometry.

    Science.gov (United States)

    Dunovská, Lenka; Cajka, Tomás; Hajslová, Jana; Holadová, Katerina

    2006-09-25

    Simple and rapid gas chromatographic (GC) method employing a high-resolution time-of-flight mass analyzer that enables direct analysis (no derivatization) of acrylamide in various heat-processed foodstuffs has been developed and validated. Co-isolation of acrylamide precursors such as sugars and asparagine, constituting the risk of results overestimation due to additional formation of analyte in hot GC injector, is avoided by the extraction with n-propanol followed by solvent exchange to acetonitrile (MeCN). Introduction of a novel purification strategy, dispersive solid phase extraction, based on addition of primary-secondary amine (PSA) sorbent into deffated extract in MeCN, provides a significant reduction of some abundant matrix co-extracts (mainly free fatty acids). Isotope dilution technique (d3-acrylamide as an internal standard) is employed for compensation of potential target analyte losses and/or matrix-inducted chromatographic response enhancement. Limits of quantifications (LOQs) ranged between 15 and 40 microg kg(-1) and recoveries were between 97 and 108% depending on the examined food matrix. The repeatability of measurements (expressed as relative standard deviation, R.S.D.) was as low as 1.9% for potato crisps containing acrylamide at a level of 1 mg kg(-1). Slightly higher values (R.S.D.<4.0%) were achieved for breakfast cereals and crisp bread with approximately 10 times lower content of this processing contaminant. Trueness of results generated by this new method was demonstrated via FAPAS (Food Analysis Performance Assessment Scheme) interlaboratory proficiency tests.

  4. Direct determination of acrylamide in food by gas chromatography-high-resolution time-of-flight mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Dunovska, Lenka [Institute of Chemical Technology, Department of Food Chemistry and Analysis, Technicka 3, 166 28 Prague 6 (Czech Republic); Cajka, Tomas [Institute of Chemical Technology, Department of Food Chemistry and Analysis, Technicka 3, 166 28 Prague 6 (Czech Republic); Hajslova, Jana [Institute of Chemical Technology, Department of Food Chemistry and Analysis, Technicka 3, 166 28 Prague 6 (Czech Republic)]. E-mail: jana.hajslova@vscht.cz; Holadova, Katerina [Institute of Chemical Technology, Department of Food Chemistry and Analysis, Technicka 3, 166 28 Prague 6 (Czech Republic)

    2006-09-25

    Simple and rapid gas chromatographic (GC) method employing a high-resolution time-of-flight mass analyzer that enables direct analysis (no derivatization) of acrylamide in various heat-processed foodstuffs has been developed and validated. Co-isolation of acrylamide precursors such as sugars and asparagine, constituting the risk of results overestimation due to additional formation of analyte in hot GC injector, is avoided by the extraction with n-propanol followed by solvent exchange to acetonitrile (MeCN). Introduction of a novel purification strategy, dispersive solid phase extraction, based on addition of primary-secondary amine (PSA) sorbent into deffated extract in MeCN, provides a significant reduction of some abundant matrix co-extracts (mainly free fatty acids). Isotope dilution technique (d{sub 3}-acrylamide as an internal standard) is employed for compensation of potential target analyte losses and/or matrix-inducted chromatographic response enhancement. Limits of quantifications (LOQs) ranged between 15 and 40 {mu}g kg{sup -1} and recoveries were between 97 and 108% depending on the examined food matrix. The repeatability of measurements (expressed as relative standard deviation, R.S.D.) was as low as 1.9% for potato crisps containing acrylamide at a level of 1 mg kg{sup -1}. Slightly higher values (R.S.D. < 4.0%) were achieved for breakfast cereals and crisp bread with approximately 10 times lower content of this processing contaminant. Trueness of results generated by this new method was demonstrated via FAPAS[reg] (Food Analysis Performance Assessment Scheme) interlaboratory proficiency tests.

  5. Molecular composition of aged secondary organic aerosol generated from a mixture of biogenic volatile compounds using ultrahigh resolution mass spectrometry

    Directory of Open Access Journals (Sweden)

    I. Kourtchev

    2015-02-01

    Full Text Available Field observations over the past decade indicate that a significant fraction of organic aerosol in remote areas may contain highly oxidised molecules. Aerosol processing or further oxidation (ageing of organic aerosol has been suggested to be responsible for their formation through heterogeneous uptake of oxidants and multigenerational oxidation of vapours by OH radicals. In this study we investigated the influence of several ageing processes on the molecular composition of secondary organic aerosols (SOA using direct infusion and liquid chromatography ultrahigh resolution mass spectrometry. SOA was formed in simulation chamber experiments from ozonolysis of a mixture of four biogenic volatile organic compounds (BVOC: α-pinene, β-pinene, Δ3-carene and isoprene. The SOA was subsequently aged under three different sets of conditions: in the dark in the presence of residual ozone, with UV irradiation and OH radicals, and using UV light only. Among all studied conditions, only OH radical-initiated ageing was found to influence the molecular composition of the aerosol and showed an increase in carbon oxidation state (OSC and elemental O/C ratios of the SOA components. None of the ageing processes produced an observable effect on the oligomers formed from ozonolysis of the BVOC mixture, which were found to be equally abundant in both "fresh" and "aged" SOA. Additional experiments using α-pinene as the sole precursor demonstrated that oligomers are an important group of compounds in SOA produced from both ozonolysis and OH radical-initiated oxidation processes; however, a completely different set of oligomers is formed under these two oxidation regimes. SOA from the OH radical-initiated α-pinene oxidation had a significantly higher overall OSC and O/C compared to that from pure ozonolysis experiments confirming that the OH radical reaction is more likely to be responsible for the occurrence of highly oxidised species in ambient biogenic SOA.

  6. High resolution mass spectrometry coupled with multivariate data analysis revealing plasma lipidomic alteration in ovarian cancer in Asian women.

    Science.gov (United States)

    Zhang, Yangyang; Liu, Yingying; Li, Lin; Wei, Jinchao; Xiong, Shaoxiang; Zhao, Zhenwen

    2016-04-01

    Ovarian cancer (OC) is the most common cause of death from gynecologic malignancies in women. The identification of reliable diagnostic biomarkers for the early detection of this deadly disease is critical for reducing the mortality rate of OC. Plasma lysophosphatidic acid (LPA) levels were increased from OC patients vs. healthy controls. Therefore, lipidomics may represent an excellent developing prospect for the discovery of diagnostic biomarkers of OC. In this study, a nontargeted lipidomics approach based on ultra performance liquid chromatography-electrospray ionization-QTOF-mass spectrometry (UPLC-ESI-QTOF-MS) combined with multivariate data analysis, including principal component analysis (PCA) and (orthogonal) partial least squared discriminant analysis [(O)PLS-DA] was applied for the investigation of potential diagnostic biomarkers in plasma of OC patients. Patients with OC could be distinguished from healthy individuals and patients with benign gynecological tumor disease by this method, which shows a significant lipid perturbation in this disease. With the assistance of high resolution and high accuracy of MS and MS/MS data, the potential markers including lysophosphatidylcholines (LPCs), phosphatidylcholines (PCs) and triacylglycerols (TGs) with specific fatty acid chains, were identified. Interestingly, LPCs were up-regulated and PCs and TGs were down-regulated, compared OC group with benign tumor and normal control groups, and the glycerophospholipid metabolism emerged as a key pathway, in particular, the phospholipase A2 (PLA2) enzyme activity, that was disregulated in the disease. This study may provide new insight into underlying mechanisms for OC and proves that MS-based lipidomics is a powerful method in discovering new potential clinical biomarkers for diseases. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. High-resolution mass spectrometric identification and quantification of glucocorticoid compounds in various wastewaters in the Netherlands.

    Science.gov (United States)

    Schriks, Merijn; van Leerdam, Jan A; van der Linden, Sander C; van der Burg, Bart; van Wezel, Annemarie P; de Voogt, Pim

    2010-06-15

    In the past two decades much research effort has focused on the occurrence, effects, and risks of estrogenic compounds. However, increasing emissions of new emerging compounds may also affect the action of hormonal pathways other than the estrogenic hormonal axis. Recently, a suite of novel CALUX bioassays has become available that enables looking further than estrogenic effects only. By employing these bioassays, we recently showed high glucocorticogenic activity in wastewaters collected at various sites in The Netherlands. However, since bioassays provide an integrated biological response, the identity of the responsible biological compounds remained unknown. Therefore, our current objective was to elucidate the chemical composition of the wastewater extracts used in our previous study by means of LC-high-resolution Orbitrap MS/MS and to determine if the compounds quantified could account for the observed glucocorticoid responsive (GR) CALUX bioassay response. The mass spectrometric analysis revealed the presence of various glucocorticoids in the range of 13-1900 ng/L. In extracts of hospital wastewater-collected prior to sewage treatment-several glucocorticoids were identified (cortisol 275-301 ng/L, cortisone 381-472 ng/L, prednisone 117-545 ng/L, prednisolone 315-1918 ng/L, and triamcinolone acetonide 14-41 ng/L) which are used to treat a great number of human pathologies. A potency balance calculation based on the instrumental analyses and relative potencies (REPs) of the individual glucocorticoids supports the conclusion that triamcinolone acetonide (REP = 1.3), dexamethasone (REP = 1), and prednisolone (REP = 0.2) are the main contributors to the glucocorticogenic activity in the investigated wastewater extracts. The action of these compounds is concentration additive and the overall glucocorticogenic activity can be explained to a fairly large extent by their contribution.

  8. 3,4-Methylenedioxypyrovalerone (MDPV) and metabolites quantification in human and rat plasma by liquid chromatography-high resolution mass spectrometry.

    Science.gov (United States)

    Anizan, Sebastien; Ellefsen, Kayla; Concheiro, Marta; Suzuki, Masaki; Rice, Kenner C; Baumann, Michael H; Huestis, Marilyn A

    2014-05-27

    Synthetic cathinones are recreational drugs that mimic the effects of illicit stimulants like cocaine, amphetamine or Ecstasy. Among the available synthetic cathinones in the United States, 3,4-methylenedioxypyrovalerone (MDPV) is commonly abused and associated with dangerous side effects. MDPV is a dopamine transporter blocker 10-fold more potent than cocaine as a locomotor stimulant in rats. Previous in vitro and in vivo studies examining MDPV metabolism reported 3,4-dihydroxypyrovalerone (3,4-catechol-PV) and 4-hydroxy-3-methoxypyrovalerone (4-OH-3-MeO-PV) as the two primary metabolites. We developed and validated a liquid chromatography-high resolution mass spectrometry method to quantify MDPV and its primary metabolites in 100 μL human and rat plasma. Plasma hydrolysis was followed by protein precipitation before analysis. Limits of detection were 0.1 μg L(-1), with linear ranges from 0.25 to 1000 μg L(-1). Process efficiency, matrix effect, total imprecision (%CV) and accuracy (%target) were 36-93%, from -8 to 12%, 2.1 to 7.3% and 86 to 109%, respectively. MDPV and metabolites were stable at room temperature for 24 h, 4 °C for 72 h and after 3 freeze-thaw cycles with less than 10% variability. Human-rat plasma cross validation demonstrated that rat plasma could be accurately quantified against a human plasma calibration curve. As proof of this method, rat plasma specimens were analyzed after intraperitoneal and subcutaneous dosing with MDPV (0.5 mg kg(-1)). MDPV, 3,4-catechol-PV and 4-OH-3-MeO-PV concentrations ranged from not detected to 107.5 μg L(-1) prior to and up to 8h after dosing. This method provides a simultaneous quantification of MDPV and two metabolites in plasma with good selectivity and sensitivity. Published by Elsevier B.V.

  9. Comparison of differential mobility spectrometry and mass spectrometry for gas chromatographic detection of ignitable liquids from fire debris using projected difference resolution.

    Science.gov (United States)

    Lu, Yao; Chen, Ping; Harrington, Peter B

    2009-08-01

    The significance of forensic arson analysis accelerates the applications of new technologies in this area. Based on the previously reported application of differential mobility spectrometry (DMS) as a detection method for gas chromatography (GC) in arson analysis, the performances of DMS and mass spectrometry (MS) were compared using a novel chemometric tool, projected difference resolutions (PDRs). The PDR results show that one-way mass spectra data exhibit higher resolution than DMS data, while total ion chromatograms from GC-DMS show higher resolution than that from GC/MS for differentiating seven kinds of ignitable liquids. Combining the information from both chromatography and spectra, two-way data always have higher resolution than one-way data for these two detection methods, and GC/MS would exhibit better performance than GC-DMS according to the minimum resolution value. To verify the PDR results, a fuzzy rule-building expert system was applied for classifying these seven kinds of ignitable liquids from fire debris based on GC-DMS and GC/MS data, respectively. The prediction accuracies were consistent with PDR results, which proved that PDR is a powerful tool in comparing the performances of different analysis methods for pattern recognition.

  10. Regional hydrologic response to climate change in the conterminous United States using high-resolution hydroclimate simulations

    Science.gov (United States)

    Naz, Bibi S.; Kao, Shih-Chieh; Ashfaq, Moetasim; Rastogi, Deeksha; Mei, Rui; Bowling, Laura C.

    2016-08-01

    Despite the fact that Global Climate Model (GCM) outputs have been used to project hydrologic impacts of climate change using off-line hydrologic models for two decades, many of these efforts have been disjointed - applications or at least calibrations have been focused on individual river basins and using a few of the available GCMs. This study improves upon earlier attempts by systematically projecting hydrologic impacts for the entire conterminous United States (US), using outputs from ten GCMs from the latest Coupled Model Intercomparison Project phase 5 (CMIP5) archive, with seamless hydrologic model calibration and validation techniques to produce a spatially and temporally consistent set of current hydrologic projections. The Variable Infiltration Capacity (VIC) model was forced with ten-member ensemble projections of precipitation and air temperature that were dynamically downscaled using a regional climate model (RegCM4) and bias-corrected to 1/24° (~ 4 km) grid resolution for the baseline (1966-2005) and future (2011-2050) periods under the Representative Concentration Pathway 8.5. Based on regional analysis, the VIC model projections indicate an increase in winter and spring total runoff due to increases in winter precipitation of up to 20% in most regions of the US. However, decreases in snow water equivalent (SWE) and snow-covered days will lead to significant decreases in summer runoff with more pronounced shifts in the time of occurrence of annual peak runoff projected over the eastern and western US. In contrast, the central US will experience year-round increases in total runoff, mostly associated with increases in both extreme high and low runoff. The projected hydrological changes described in this study have implications for various aspects of future water resource management, including water supply, flood and drought preparation, and reservoir operation.

  11. PCDD, PCDF, AND DL-PCB analysis in food: performance evaluation of the high-resolution gas chromatography/low-resolution tandem mass spectrometry technique using consensus-based samples.

    Science.gov (United States)

    Ingelido, Anna Maria; Brambilla, Gianfranco; Abballe, Annalisa; di Domenico, Alessandro; Fulgenzi, Anna Rita; Iacovella, Nicola; Iamiceli, Anna Laura; Valentini, Silvia; De Felip, Elena

    2012-02-15

    Due to safety concerns regarding dietary exposure to POPs, regulatory bodies are issuing detailed guidelines for testing for polychlorodibenzodioxins (PCDDs) and polychlorodibenzofurans (PCDFs) ('dioxins') and dioxin-like (DL)-PCBs in foods of animal origin. Determination of the aforesaid chemicals at regulatory levels requires highly selective and sensitive testing techniques. The new generation of low-resolution mass spectrometers (triple quadrupoles) allows very low levels of quantification to be reached (in the order of tens of femtograms), thus suggesting a potential for their application in food and feed analysis. The performance of the low-resolution tandem mass spectrometry (LRMS/MS) approach with triple quadrupoles was assessed on a qualified set of food samples from proficiency tests (PTs) and defense analysis. Accuracy was tested comparing the results with data from high-resolution mass spectrometry (HRMS) and with consensus values from PTs. The cumulative TEQ results were characterized by deviations not exceeding 15% of PCDD + PCDF, DL-PCB, and PCDD + PCDF + DL-PCB (TEQ(TOT)) reference consensus values (sample TEQ(TOT) range, 2.29-25.1 pgWHO-TEQ(97)/g fat). Congener analytical variabilities did not influence significantly the WHO-TEQ(97) outcome of the corresponding sample. This preliminary performance evaluation highlights the potential of LRMS/MS as a routine technique for quantitative analysis of PCDDs, PCDFs, and DL-PCBs in food.

  12. Sublimation of new matrix candidates for high spatial resolution imaging mass spectrometry of lipids: enhanced information in both positive and negative polarities after 1,5-diaminonapthalene deposition.

    Science.gov (United States)

    Thomas, Aurélien; Charbonneau, Jade Laveaux; Fournaise, Erik; Chaurand, Pierre

    2012-02-21

    Matrix sublimation has demonstrated to be a powerful approach for high-resolution matrix-assisted laser desorption ionization (MALDI) imaging of lipids, providing very homogeneous solvent-free deposition. This work presents a comprehensive study aiming to evaluate current and novel matrix candidates for high spatial resolution MALDI imaging mass spectrometry of lipids from tissue section after deposition by sublimation. For this purpose, 12 matrices including 2,5-dihydroxybenzoic acid (DHB), sinapinic acid (SA), α-cyano-4-hydroxycinnamic acid (CHCA), 2,6-dihydroxyacetphenone (DHA), 2',4',6'-trihydroxyacetophenone (THAP), 3-hydroxypicolinic acid (3-HPA), 1,8-bis(dimethylamino)naphthalene (DMAN), 1,8,9-anthracentriol (DIT), 1,5-diaminonapthalene (DAN), p-nitroaniline (NIT), 9-aminoacridine (9-AA), and 2-mercaptobenzothiazole (MBT) were investigated for lipid detection efficiency in both positive and negative ionization modes, matrix interferences, and stability under vacuum. For the most relevant matrices, ion maps of the different lipid species were obtained from tissue sections at high spatial resolution and the detected peaks were characterized by matrix-assisted laser desorption ionization time-of-flight/time-of-flight (MALDI-TOF/TOF) mass spectrometry. First proposed for imaging mass spectrometry (IMS) after sublimation, DAN has demonstrated to be of high efficiency providing rich lipid signatures in both positive and negative polarities with high vacuum stability and sub-20 μm resolution capacity. Ion images from adult mouse brain were generated with a 10 μm scanning resolution. Furthermore, ion images from adult mouse brain and whole-body fish tissue sections were also acquired in both polarity modes from the same tissue section at 100 μm spatial resolution. Sublimation of DAN represents an interesting approach to improve information with respect to currently employed matrices providing a deeper analysis of the lipidome by IMS.

  13. Mass Transport Complexes in bacini confinati a controllo strutturale: l'Unità Epiligure di Specchio (Appennino Settentrionale)

    OpenAIRE

    Ogata, Kei

    2010-01-01

    Il recente incremento dell’esplorazione geofisica dei margini continentali e il concomitante sviluppo di tecnologie d’indagine, sismiche ed acustiche, sempre più accurate, hanno rivelato la comune presenza di vasti accumuli di sedimenti rimobilizzati a causa di franamenti sottomarini, e comunemente identificati con il termine di Mass Transport Deposit o Complex (MTD e MTC, rispettivamente). Attualmente, queste unità sono intensamente studiate non solo per ragioni strettamente scientifiche,...

  14. Energy and mass balances in multiple-effect upward solar distillers with air flow through the last-effect unit

    Energy Technology Data Exchange (ETDEWEB)

    Homing Yeh; Chiidong Ho [Tamkang Univ. Tamsui, Dept. of Chemical Engineering, Taipei Hsien (Taiwan)

    2000-04-01

    Considerable improvement in productivity may be obtained if water vapor in the last-effect unit is carried away directly by flowing air. The theory of a closed-type upward multiple-effect solar distiller has been modified to that of an open-type device, and the energy and mass balances have been derived. The production rate of distilled water for each effect under various climate, design, and operational conditions may be predicted by simultaneously solving the appropriate equations. (Author)

  15. Kepler-47 Circumbinary Planets obey Quantization of Angular Momentum per Unit Mass predicted by Quantum Celestial Mechanics (QCM

    Directory of Open Access Journals (Sweden)

    Potter F.

    2014-01-01

    Full Text Available The Kepler-47 circumbinary system has three known planets orbiting its binary star barycenter and therefore can provide a precision test of the Quantum Celestial Mechan- ics (QCM prediction of the quantization of angular momentum per unit mass in all gravitationally bound systems. Two of the planets are in the Habitable Zone (HZ, so system stability can be a primary concern. QCM may be a major contributor to the stability of this system.

  16. Development of High Resolution Resonance Ionization Mass Spectrometry for Neutron Dosimetry Technique with93Nb(n,n'93mNb Reaction

    Directory of Open Access Journals (Sweden)

    Tomita Hideki

    2016-01-01

    Full Text Available We have proposed an advanced technique to measure the 93mNb yield precisely by Resonance Ionization Mass Spectrometry, instead of conventional characteristic X-ray spectroscopy. 93mNb-selective resonance ionization is achievable by distinguishing the hyperfine splitting of the atomic energy levels between 93Nb and 93mNb at high resolution. In advance of 93mNb detection, we could successfully demonstrate high resolution resonant ionization spectroscopy of stable 93Nb using an all solid-state, narrow-band and tunable Ti:Sapphire laser system operated at 1 kHz repetition rate.

  17. Mass and number size distributions of emitted particulates at five important operation units in a hazardous industrial waste incineration plant.

    Science.gov (United States)

    Lin, Chi-Chi; Huang, Hsiao-Lin; Hsiao, Wen-Yuan

    2016-01-01

    Past studies indicated particulates generated by waste incineration contain various hazardous compounds. The aerosol characteristics are very important for particulate hazard control and workers' protection. This study explores the detailed characteristics of emitted particulates from each important operation unit in a rotary kiln-based hazardous industrial waste incineration plant. A dust size analyzer (Grimm 1.109) and a scanning mobility particle sizer (SMPS) were used to measure the aerosol mass concentration, mass size distribution, and number size distribution at five operation units (S1-S5) during periods of normal operation, furnace shutdown, and annual maintenance. The place with the highest measured PM10 concentration was located at the area of fly ash discharge from air pollution control equipment (S5) during the period of normal operation. Fine particles (PM2.5) constituted the majority of the emitted particles from the incineration plant. The mass size distributions (elucidated) made it clear that the size of aerosols caused by the increased particulate mass, resulting from work activities, were mostly greater than 1.5 μm. Whereas the number size distributions showed that the major diameters of particulates that caused the increase of particulate number concentrations, from work activities, were distributed in the sub micrometer range. The process of discharging fly ash from air pollution control equipment can significantly increase the emission of nanoparticles. The mass concentrations and size distributions of emitted particulates were different at each operation unit. This information is valuable for managers to take appropriate strategy to reduce the particulate emission and associated worker exposure.

  18. Further development and application of a mobile multiple-reflection time-of-flight mass spectrometer for analytical high-resolution tandem mass spectrometry

    OpenAIRE

    Lippert, Wayne

    2016-01-01

    In this work, a mobile multiple-reflection time-of-flight mass spectrometer (MR-TOF-MS) for analytical mass spectrometry was enhanced in many important aspects. Technical as well as software-based improvements have been added to the instrument, thus greatly increasing its performance and applicability. Changes have been applied to the whole beam preparation system of the MR-TOF-MS. In this context, the electronic setup was completely overhauled and a quadrupole mass filter was commissioned. C...

  19. Mass Distribution Measurement of 252Cf Spontaneous Fission

    Institute of Scientific and Technical Information of China (English)

    LIU; Shi-long; YANG; Yi; ZHANG; Chun-li; HAN; Hong-yin

    2015-01-01

    The E-v method of measuring the kinetic energy(E)and velocity(v)of outgoing fission products has been utilized,with the goal of measuring the mass resolution better than 1atomic mass units(amu),and could identify every mass for light fission products of unsymmetrical fission.This work measured mass yield distribution

  20. USGS Small-scale Dataset - Color Conterminous United States Shaded Relief - 200-Meter Resolution, Albers projection 200603 GeoTIFF

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — The color conterminous United States shaded relief data were derived from National Elevation Dataset (NED) data, and show the terrain of the conterminous United...

  1. USGS Small-scale Dataset - Grayscale Conterminous United States Shaded Relief - 200-Meter Resolution, Albers projection 200603 GeoTIFF

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — The grayscale conterminous United States shaded relief data were derived from National Elevation Dataset (NED) data, and show the terrain of the conterminous United...

  2. USGS Small-scale Dataset - Grayscale Conterminous United States Shaded Relief - 200-Meter Resolution 200509 GeoTIFF

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — The grayscale conterminous United States shaded relief data were derived from National Elevation Dataset (NED) data, and show the terrain of the conterminous United...

  3. USGS Small-scale Dataset - Color Conterminous United States Shaded Relief - 200-Meter Resolution 200512 GeoTIFF

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — The color conterminous United States shaded relief data were derived from National Elevation Dataset (NED) data, and show the terrain of the conterminous United...

  4. Detection of Gelatin Adulteration in Traditional Chinese Medicine: Analysis of Deer-Horn Glue by Rapid-Resolution Liquid Chromatography-Triple Quadrupole Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Jia Chen

    2015-01-01

    Full Text Available Simultaneous identification of donkey-hide gelatin and bovine-hide gelatin in deer-horn glue was established by rapid-resolution liquid chromatography-triple quadrupole mass spectrometry. Water containing 1% NH4HCO3 was used for sample dissolution and trypsin was used for hydrolysis of the gelatins. After separation by a SB-C18 reversed-phase analytical column, collagen marker peptides were detected by mass spectrometry in positive electrospray ionization mode with multiple reaction monitoring. The method was specific, precise and reliable, and suitable for detection of adulterants derived from donkey-hide gelatin and bovine-hide gelatin in deer-horn glue.

  5. Computer programs for the interpretation of low resolution mass spectra: Program for calculation of molecular isotopic distribution and program for assignment of molecular formulas

    Science.gov (United States)

    Miller, R. A.; Kohl, F. J.

    1977-01-01

    Two FORTRAN computer programs for the interpretation of low resolution mass spectra were prepared and tested. One is for the calculation of the molecular isotopic distribution of any species from stored elemental distributions. The program requires only the input of the molecular formula and was designed for compatability with any computer system. The other program is for the determination of all possible combinations of atoms (and radicals) which may form an ion having a particular integer mass. It also uses a simplified input scheme and was designed for compatability with any system.

  6. Confirmation of pinnatoxins and spirolides in shellfish and passive samplers from Catalonia (Spain) by liquid chromatography coupled with triple quadrupole and high-resolution hybrid tandem mass spectrometry.

    Science.gov (United States)

    García-Altares, María; Casanova, Alexis; Bane, Vaishali; Diogène, Jorge; Furey, Ambrose; de la Iglesia, Pablo

    2014-06-01

    Cyclic imines are lipophilic marine toxins that bioaccumulate in seafood. Their structure comprises a cyclic-imino moiety, responsible for acute neurotoxicity in mice. Cyclic imines have not been linked yet to human poisonings and are not regulated in Europe, although the European Food Safety Authority requires more data to perform a conclusive risk assessment for consumers. This work presents the first detection of pinnatoxin G (PnTX-G) in Spain and 13-desmethyl spirolide C (SPX-1) in shellfish from Catalonia (Spain, NW Mediterranean Sea). Cyclic imines were found at low concentrations (2 to 60 µg/kg) in 13 samples of mussels and oysters (22 samples analyzed). Pinnatoxin G has been also detected in 17 seawater samples (out of 34) using solid phase adsorption toxin tracking devices (0.3 to 0.9 µg/kg-resin). Pinnatoxin G and SPX-1 were confirmed with both low and high resolution (<2 ppm) mass spectrometry by comparison of the response with that from reference standards. For other analogs without reference standards, we applied a strategy combining low resolution MS with a triple quadrupole mass analyzer for a fast and reliable screening, and high resolution MS LTQ Orbitrap® for unambiguous confirmation. The advantages and limitations of using high resolution MS without reference standards were discussed.

  7. The coupling of direct analysis in real time ionization to Fourier transform ion cyclotron resonance mass spectrometry for ultrahigh-resolution mass analysis.

    Science.gov (United States)

    Rummel, Julia L; McKenna, Amy M; Marshall, Alan G; Eyler, John R; Powell, David H

    2010-03-01

    Direct Analysis in Real Time (DART) is an ambient ionization technique for mass spectrometry that provides rapid and sensitive analyses with little or no sample preparation. DART has been reported primarily for mass analyzers of low to moderate resolving power such as quadrupole ion traps and time-of-flight (TOF) mass spectrometers. In the current work, a custom-built DART source has been successfully coupled to two different Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometers for the first time. Comparison of spectra of the isobaric compounds, diisopropyl methylphosphonate and theophylline, acquired by 4.7 T FT-ICR MS and TOF MS, demonstrates that the TOF resolving power can be insufficient for compositionally complex samples. 9.4 T FT-ICR MS yielded the highest mass resolving power yet reported with DART ionization for 1,2-benzanthracene and 9,10-diphenylanthracene. Polycyclic aromatic hydrocarbons exhibit a spatial dependence in ionization mechanisms between the DART source and the mass spectrometer. The feasibility of analyzing a variety of samples was established with the introduction and analysis of food products and crude oil samples. DART FT-ICR MS provides complex sample analysis that is rapid, highly selective and information-rich, but limited to relatively low-mass analytes.

  8. A High-Resolution Transmission-Type (TT) Phaser Based on Reflection-Type (RT) Units for Radio Analog Signal Processing (R-ASP)

    CERN Document Server

    Zou, Lianfeng

    2014-01-01

    A high Radio Analog Signal Processing (R-ASP) resolution transmission-type (TT) phaser based on reflection-type (RT) phaser units is introduced, theoretically studied and experimentally demonstrated. It is first shown that RT phasers inherently exhibit higher R-ASP resolution than their TT counterparts because their group delay swing is proportional to the reflection coefficient associated with a resonator coupling mechanism (admittance inverter), easy to maximize towards unity, rather than to a coupled-line coupling coefficient, typically restricted to values will inferior to unity, as in the RT case. Moreover, a detailed sensitivity analysis reveals that the proposed phaser is simultaneously features high R-ASP resolution and low sensitivity to fabrication tolerance, which makes it an ideal solution for R-ASP. The proposed phaser exhibits a 5 ns group delay swing over a fractional bandwidth of about 50% around 4 GHz.

  9. First performance results of a mobile high-resolution MR-ToF mass spectrometer for in-situ analytical mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Lang, Johannes; Ebert, Jens [II. Physikalisches Institut, JLU Giessen (Germany); Dickel, Timo; Plass, Wolfgang; Geissel, Hans; Haettner, Emma; Scheidenberger, Christoph [II. Physikalisches Institut, JLU Giessen (Germany); GSI, Darmstadt (Germany); Yavor, Mikhail [RAS St. Petersburg (Russian Federation)

    2012-07-01

    A mobile multiple-reflection time-of-flight mass spectrometer (MR-TOF-MS) has been designed, built and commissioned. While other mobile mass spectrometers are restricted to low or medium mass resolving power, this MR-TOF-MS allows for the first time for a mass resolving power exceeding 100.000 and a sub ppm accuracy in a transportable format. It can thus resolve isobars and enables to accurately determine the composition and structure of biomolecules. An atmospheric pressure interface provides compatibility to various atmospheric ion sources. The mass spectrometer part comprises an RFQ mass filter, ion cooler, ion trap, time-of-flight analyzer and detector. Supply electronics, DAQ and control system are mounted together with the spectrometer into a single frame with a total volume of only 0.8 m{sup 3}. First results with the MR-TOF-MS are presented, and an overview of envisaged life science applications is given, such as realtime tissue recognition in electrosurgery, identification of mycotoxins and analysis of soil samples for environmental studies.

  10. Representation of People of Asian Descent in Mainstream Mass Media within the United States

    Science.gov (United States)

    Kim, Younghan

    2013-01-01

    The public school classroom in the United States has been getting more diverse, linguistically and ethnically. Immigrant and second/third generation students learn American culture and norms from messages conveyed through mainstream media like internet, advertisements, films, newspapers, TV, and magazines. Their self-perceptions, perspectives…

  11. [Application of gas chromatography-high resolution quadrupole time of flight mass spectrometry to the analysis of benzaldehyde, benzyl alcohol acetophenone and phenylacetaldehyde in complex aromatic samples].

    Science.gov (United States)

    Liu, Junyan; Cao, Zhe; Li, Jiwen; Wang, Zheming; Wang, Chuan; Gu, Songyuan

    2015-02-01

    The study focuses on the quantitative analytical characterization of benzaldehyde, benzyl alcohol, acetophenone and phenylacetaldehyde in complex aromatic samples by gas chromatography-high resolution quadrupole time of flight mass spectrometry (GC-QTOF MS). The four compounds in real sample were accurately qualified and quantified through a comprehensive analysis of the GC retention times and the accurate masses of the ion fragments obtained by the high resolution MS. The new method therefore effectively avoids the interference of the real sample substrate, which reduces the accuracy of the analysis results. The peak area of the characteristic ion fragment for each compound was used for quantitation calculation. The MS signal responses of the four compounds showed good linear relationships with the corresponding mass concentrations and the linear regression coefficients were greater than 0. 99. The method recoveries were 87. 97% - 103.01%. The limits of detection (LODs) were 0. 01, 0. 03, 0. 02 and 0. 01 mg/L for benzaldehyde, benzyl alcohol, acetophenone and phenylacetaldehyde respectively. The contents of the four compounds in three real samples were analyzed. The study provided a new strategy for oxygenate analysis in complex aromatic samples using GC-QTOF MS. By measuring the accurate masses, the new method reduces the reliance on chromatographic separation ability and makes up the shortcomings of the traditional GC-MS methods.

  12. Biodegradation of carbamazepine and clarithromycin by Trichoderma harzianum and Pleurotus ostreatus investigated by liquid chromatography - high-resolution tandem mass spectrometry (FTICR MS-IRMPD).

    Science.gov (United States)

    Buchicchio, Alessandro; Bianco, Giuliana; Sofo, Adriano; Masi, Salvatore; Caniani, Donatella

    2016-07-01

    In this study, the capability of pharmaceutical biodegradation of fungus Trichoderma harzianum was evaluated through the comparison with the well-known biodegradation capability of white-rot fungus Pleurotus ostreatus. The study was performed in aqueous phase under aerobic conditions, using two of the most frequently detected drugs in water bodies: carbamazepine and clarithromycin, with concentrations commonly found in treated wastewater (4μg/l and 0.03μg/l respectively). For the first time, we demonstrated that T. harzianum is able to remove carbamazepine and clarithromycin. The analyses were performed by reversed-phase liquid chromatography/mass spectrometry, using high-resolution Fourier-transform ion cyclotron resonance mass spectrometry upon electrospray ionization in positive ion mode. The high selectivity and mass accuracy provided by high-resolution mass spectrometry, allowed us to identify some unknown metabolites. On the basis of our study, the major metabolites detected in liquid culture treated by T. harzianum were: 14-hydroxy-descladinosyl- and descladinosyl-clarithromycin, which are pharmacologically inactive products not dangerous for the environment. Copyright © 2016 Elsevier B.V. All rights reserved.

  13. The Role of Ultrahigh Resolution Fourier Transform Mass Spectrometry (FT-MS) in Astrobiology-Related Research: Analysis of Meteorites and Tholins.

    Science.gov (United States)

    Somogyi, Árpád; Thissen, Roland; Orthous-Daunay, Francois-Régis; Vuitton, Véronique

    2016-03-24

    It is an important but also a challenging analytical problem to understand the chemical composition and structure of prebiotic organic matter that is present in extraterrestrial materials. Its formation, evolution and content in the building blocks ("seeds") for more complex molecules, such as proteins and DNA, are key questions in the field of exobiology. Ultrahigh resolution mass spectrometry is one of the best analytical techniques that can be applied because it provides reliable information on the chemical composition and structure of individual components of complex organic mixtures. Prebiotic organic material is delivered to Earth by meteorites or generated in laboratories in simulation (model) experiments that mimic space or atmospheric conditions. Recent representative examples for ultrahigh resolution mass spectrometry studies using Fourier-transform (FT) mass spectrometers such as Orbitrap and ion cyclotron resonance (ICR) mass spectrometers are shown and discussed in the present article, including: (i) the analysis of organic matter of meteorites; (ii) modeling atmospheric processes in ICR cells; and (iii) the structural analysis of laboratory made tholins that might be present in the atmosphere and surface of Saturn's largest moon, Titan.

  14. The Role of Ultrahigh Resolution Fourier Transform Mass Spectrometry (FT-MS in Astrobiology-Related Research: Analysis of Meteorites and Tholins

    Directory of Open Access Journals (Sweden)

    Árpád Somogyi

    2016-03-01

    Full Text Available It is an important but also a challenging analytical problem to understand the chemical composition and structure of prebiotic organic matter that is present in extraterrestrial materials. Its formation, evolution and content in the building blocks (“seeds” for more complex molecules, such as proteins and DNA, are key questions in the field of exobiology. Ultrahigh resolution mass spectrometry is one of the best analytical techniques that can be applied because it provides reliable information on the chemical composition and structure of individual components of complex organic mixtures. Prebiotic organic material is delivered to Earth by meteorites or generated in laboratories in simulation (model experiments that mimic space or atmospheric conditions. Recent representative examples for ultrahigh resolution mass spectrometry studies using Fourier-transform (FT mass spectrometers such as Orbitrap and ion cyclotron resonance (ICR mass spectrometers are shown and discussed in the present article, including: (i the analysis of organic matter of meteorites; (ii modeling atmospheric processes in ICR cells; and (iii the structural analysis of laboratory made tholins that might be present in the atmosphere and surface of Saturn’s largest moon, Titan.

  15. Characterization of submicron aerosols at a rural site in Pearl River Delta of China using an Aerodyne High-Resolution Aerosol Mass Spectrometer

    Directory of Open Access Journals (Sweden)

    X.-F. Huang

    2010-11-01

    Full Text Available The Pearl River Delta (PRD region in South China is one of the most economically developed regions in China, but it is also noted for its severe air pollution due to industrial/metropolitan emissions. In order to continuously improve the understanding and quantification of air pollution in this region, an intensive campaign was executed in PRD during October–November 2008. Here, we report and analyze Aerodyne High-Resolution Aerosol Mass Spectrometer measurements at Kaiping, a rural site downwind of the highly-polluted central PRD area, to characterize the general features of submicron particulate pollution in the regional air. The mean measured PM1 mass concentration was 33.1 ± 18.1 μg m−3 during the campaign and composed of organic matter (33.8%, sulfate (33.7%, ammonium (14.0%, nitrate (10.7%, black carbon (6.7%, and chloride (1.1%, which is characterized by high fractions of inorganic ions due to huge emissions of SO2 and NOx in PRD. The average size distributions of the species (except BC were all dominated by an accumulation mode peaking at ~450 nm in vacuum aerodynamic diameter. Calculations based on high-resolution organic mass spectra indicate that C, H, O, and N on average contributed 56.6, 7.0, 35.1, and 1.3% to the total organic mass, respectively, corresponding to an organic matter mass to organic carbon mass ratio (OM/OC of 1.77 ± 0.08. Based on the high-resolution organic mass spectral dataset observed, Positive Matrix Factorization (PMF analysis differentiated the organic aerosol into three components, i.e., biomass burning (BBOA and two oxygenated (LV-OOA and SV-OOA organic aerosols, which on average accounted for 24.5, 39.6 and 35.8% of the total organic mass, respectively. The BBOA showed strong features of biomass burning emissions and has been mainly attributed to field rice straw burning after harvest. The LV-OOA and SV-OOA were found to correspond to more aged (and thus

  16. High resolution LC-ESI-TOF-mass spectrometry method for fast separation, identification, and quantification of 12 isoflavones in soybeans and soybean products.

    Science.gov (United States)

    Lee, Mi Jin; Chung, Ill-Min; Kim, Hunjung; Jung, Mun Yhung

    2015-06-01

    A high resolution LC-ESI-TOF-MS analytical method was established for the rapid isolation, identification, and quantification of 12 isoflavones in soybean and soybean products. Individual isoflavones were identified on the basis of the accurate mass data of their respective protonated mass ions, Na or K adduct ions, fragment ions, and isotope ion patterns. The protonated mass ions of isoflavones were extracted for their quantification in soybean products. Twelve different isoflavones in the soybean products were fully separated, identified and quantified within 12min separation time. The established LC-TOF/MS was an effective analytical method for the simultaneous characterization and quantification of isoflavones with exceptionally short analytical time, high selectivity, a high linearity (r(2)>0.992) in a wide range, low LOD and LOQ, high precision, inter-and intra-day repeatability, and no significant matrix effect. Furthermore, it requires simple sample preparation procedure (solvent extraction, dilution, and syringe filtration).

  17. Dynamic Cluster Analysis: An Unbiased Method for Identifying A+2 Element Containing Compounds in Liquid Chromatographic High-Resolution TOF Mass Spectrometric Data

    DEFF Research Database (Denmark)

    Andersen, Aaron John Christian; Hansen, Per Juel; Jørgensen, Kevin

    2016-01-01

    Dynamic Cluster Analysis (DCA) is an automated, unbiased technique which can identify Cl, Br, S, and other A+2 element containing metabolites in liquid chromatographic high resolution mass spectrometric data. DCA is based on three features, primarily the previously unutilised A+1 to A+2 isotope...... cluster spacing which is a strong classifier in itself, but improved with the addition of the monoisotopic mass, and the well-known A:A+2 intensity ratio. Utilizing only the A+1 to A+2 isotope cluster spacing and the monoisotopic mass it was possible to filter a chromatogram for metabolites which contain...... Cl, Br, and S. Screening simulated isotope patterns of the Antibase Natural Products Database it was determined that the A+1 to A+2 isotope cluster spacing can be used to correctly classify 97.4% of molecular formulas containing these elements, only misclassifying a few metabolites which were either...

  18. An Examination of Carbon Monoxide and Organic Aerosol Mass Sources in the Southeastern United States during the SENEX Project

    Science.gov (United States)

    Middlebrook, A. M.; Angevine, W. M.; Brioude, J. F.; Brock, C. A.; De Gouw, J. A.; Gilman, J.; Graus, M.; Hanisco, T. F.; Holloway, J. S.; Horowitz, L. W.; Kaiser, J.; Keutsch, F. N.; Lerner, B. M.; Liao, J.; Mao, J.; Trainer, M.; Warneke, C.; Welti, A.; Wolfe, G. M., Jr.

    2014-12-01

    The NOAA Southeast Nexus (SENEX) project occurred during the summer of 2013 over the southeastern United States and involved studying the interactions between natural and anthropogenic emissions at the nexus of climate change and air quality. As part of the project, a suite of instruments for aerosol and gas-phase species was deployed on the NOAA WP-3D aircraft and models were used to calculate trace gas and aerosol species in the region and along the aircraft flight tracks. Throughout the study, the measured non-refractory submicron aerosol mass was dominated by organic material (58% +/- 9%) with smaller contributions from sulfate (27% +/- 8%), ammonium (10% +/- 3%), nitrate (3% +/- 1%), and chloride (0.1% +/- 0.1%). Here we examine the influence of urban emissions on the organic aerosol (OA) mass in regions characterized by higher and lower biogenic emissions. For the air around and downwind of urban areas, OA mass is highly correlated with carbon monoxide (CO), a tracer of anthropogenic emissions as well as an oxidation product of isoprene, a biogenic species. The slope of this correlation is roughly 0.15 micrograms per standard cubic meter per ppbv, which is significantly higher than observed in prior studies downwind of urban areas. The enhancement in OA mass relative to the enhancement in CO is independent of the concentration of biogenic species. In contrast, formaldehyde enhancements are clearly higher in the presence of biogenic species in agreement with the NOAA GFDL AM3 model. Downwind from the urban areas, CO and OA mass were not strongly enhanced relatively to a region-wide enhancement in these species that can only be explained from the accumulation of emissions in the eastern U.S. for several days. Back-trajectories of air parcels with emissions from biogenic and anthropogenic sources will be examined to elucidate the impact of both sources on CO and OA mass.

  19. The Effect of Fuel Mass Fraction on the Combustion and Fluid Flow in a Sulfur Recovery Unit Thermal Reactor

    Directory of Open Access Journals (Sweden)

    Chun-Lang Yeh

    2016-11-01

    Full Text Available Sulfur recovery unit (SRU thermal reactors are negatively affected by high temperature operation. In this paper, the effect of the fuel mass fraction on the combustion and fluid flow in a SRU thermal reactor is investigated numerically. Practical operating conditions for a petrochemical corporation in Taiwan are used as the design conditions for the discussion. The simulation results show that the present design condition is a fuel-rich (or air-lean condition and gives acceptable sulfur recovery, hydrogen sulfide (H2S destruction, sulfur dioxide (SO2 emissions and thermal reactor temperature for an oxygen-normal operation. However, for an oxygen-rich operation, the local maximum temperature exceeds the suggested maximum service temperature, although the average temperature is acceptable. The high temperature region must be inspected very carefully during the annual maintenance period if there are oxygen-rich operations. If the fuel mass fraction to the zone ahead of the choke ring (zone 1 is 0.0625 or 0.125, the average temperature in the zone behind the choke ring (zone 2 is higher than the zone 1 average temperature, which can damage the downstream heat exchanger tubes. If the zone 1 fuel mass fraction is reduced to ensure a lower zone 1 temperature, the temperature in zone 2 and the heat exchanger section must be monitored closely and the zone 2 wall and heat exchanger tubes must be inspected very carefully during the annual maintenance period. To determine a suitable fuel mass fraction for operation, a detailed numerical simulation should be performed first to find the stoichiometric fuel mass fraction which produces the most complete combustion and the highest temperature. This stoichiometric fuel mass fraction should be avoided because the high temperature could damage the zone 1 corner or the choke ring. A higher fuel mass fraction (i.e., fuel-rich or air-lean condition is more suitable because it can avoid deteriorations of both zone 1

  20. Unit operations for gas-liquid mass transfer in reduced gravity environments

    Science.gov (United States)

    Pettit, Donald R.; Allen, David T.

    1992-01-01

    Basic scaling rules are derived for converting Earth-based designs of mass transfer equipment into designs for a reduced gravity environment. Three types of gas-liquid mass transfer operations are considered: bubble columns, spray towers, and packed columns. Application of the scaling rules reveals that the height of a bubble column in lunar- and Mars-based operations would be lower than terrestrial designs by factors of 0.64 and 0.79 respectively. The reduced gravity columns would have greater cross-sectional areas, however, by factors of 2.4 and 1.6 for lunar and Martian settings. Similar results were obtained for spray towers. In contract, packed column height was found to be nearly independent of gravity.

  1. Active damping control unit using a small scale proof mass electrodynamic actuator.

    Science.gov (United States)

    González Díaz, Cristóbal; Paulitsch, Christoph; Gardonio, Paolo

    2008-08-01

    This paper presents a study on the design and use of a small scale proof mass electrodynamic actuator, with a low mounting resonance frequency, for velocity feedback control on a thin rectangular panel. A stability-performance formula is derived, which can be effectively used to assess the down scaling effects on the stability and control performance of the feedback loop. The design and tests of a velocity feedback loop with a prototype small scale proof mass actuator are also presented. When a feedback control having a gain margin of about 6 dB is implemented, so that there is little control spillover effect around the fundamental resonance of the actuator, reductions of vibration between 5 dB and 10 dB in the frequency band between 80 Hz and 250 Hz have been measured at the control position.

  2. Mass Casualty Decontamination in the United States: An Online Survey of Current Practice.

    Science.gov (United States)

    Power, Sarah; Symons, Charles; Carter, Holly; Jones, Emma; Amlôt, Richard; Larner, Joanne; Matar, Hazem; Chilcott, Robert P

    2016-01-01

    Mass casualty decontamination is a public health intervention that would be employed by emergency responders following a chemical, biological, or radiological incident. The decontamination of large numbers of casualties is currently most often performed with water to remove contaminants from the skin surface. An online survey was conducted to explore US fire departments' decontamination practices and their preparedness for responding to incidents involving mass casualty decontamination. Survey respondents were asked to provide details of various aspects of their decontamination procedures, including expected response times to reach casualties, disrobing procedures, approaches to decontamination, characteristics of the decontamination showering process, provision for special populations, and any actions taken following decontamination. The aim of the survey was to identify any differences in the way in which decontamination guidance is implemented across US states. Results revealed that, in line with current guidance, many US fire departments routinely use the "ladder-pipe system" for conducting rapid, gross decontamination of casualties. The survey revealed significant variability in ladder-pipe construction, such as the position and number of fire hoses used. There was also variability in decontamination characteristics, such as water temperature and water pressure, detergent use, and shower duration. The results presented here provide important insights into the ways in which implementation of decontamination guidance can vary between US states. These inconsistencies are thought to reflect established perceived best practices and local adaptation of response plans to address practical and logistical constraints. These outcomes highlight the need for evidence-based national guidelines for conducting mass casualty decontamination.

  3. Body mass index and overweight in adolescents in 13 European countries, Israel, and the United States

    DEFF Research Database (Denmark)

    Lissau, Inge; Overpeck, Mary D; Ruan, W June

    2004-01-01

    in 1997-1998 by means of identical data collection methods. SETTING: Austria, Czech Republic, Denmark, Flemish Belgium, Finland, France, Germany, Greece, Lithuania, Ireland, Israel, Portugal, Slovakia, Sweden, and the United States. PARTICIPANTS: A total of 29 242 boys and girls, aged 13 and 15 years....... MAIN OUTCOME MEASURES: The BMI, BMI at or above the 85th centile, and BMI at or above the 95th centile (overweight) from self-reported height and weight. RESULTS: The highest prevalence of overweight was found in the United States and the lowest in Lithuania. On the basis of the study reference...... standard, the prevalence of overweight (percentage) in the United States was 12.6% in 13-year-old boys, 10.8% in 13-year-old girls, 13.9% in 15-year-old boys, and 15.1% in 15-year-old girls, all significantly increased. Prevalence of overweight in Lithuania was significantly below the expected 5%, with 1...

  4. (Un)targeted Scanning of Locks of Hair for Drugs of Abuse by Direct Analysis in Real Time-High-Resolution Mass Spectrometry.

    Science.gov (United States)

    Duvivier, Wilco F; van Putten, Marc R; van Beek, Teris A; Nielen, Michel W F

    2016-02-16

    Forensic hair evidence can be used to obtain retrospective timelines of drug use by analysis of hair segments. However, this is a laborious and time-consuming process, and mass spectrometric (MS) imaging techniques, which show great potential for single-hair targeted analysis, are less useful due to differences in hair growth rate between individual hairs. As an alternative, a fast untargeted analysis method was developed that uses direct analysis in real time-high-resolution mass spectrometry (DART-HRMS) to longitudinally scan intact locks of hair without extensive sample preparation or segmentation. The hair scan method was validated for cocaine against an accredited liquid chromatography/tandem mass spectrometry (LC/MS/MS) method. The detection limit for cocaine in hair was found to comply with the cutoff value of 0.5 ng/mg recommended by the Society of Hair Testing; that is, the DART hair scan method is amenable to forensic cases. Under DART conditions, no significant thermal degradation of cocaine occurred. The standard DART spot size of 5.1 ± 1.1 mm could be improved to 3.3 ± 1.0 mm, corresponding to approximately 10 days of hair growth, by using a high spatial resolution exit cone. By use of data-dependent product ion scans, multiple drugs of abuse could be detected in a single drug user hair scan with confirmation of identity by both exact mass and MS/HRMS fragmentation patterns. Furthermore, full-scan high-resolution data were retrospectively interrogated versus a list of more than 100 compounds and revealed additional hits and temporal profiles in good correlation with reported drug use.

  5. Determination of polar pesticides in olive oil and olives by hydrophilic interaction liquid chromatography coupled to tandem mass spectrometry and high resolution mass spectrometry.

    Science.gov (United States)

    Nortes-Méndez, Rocío; Robles-Molina, José; López-Blanco, Rafael; Vass, Andrea; Molina-Díaz, Antonio; Garcia-Reyes, Juan F

    2016-09-01

    This article reports the development of two HPLC-MS methods for the determination of polar pesticides in olive oil and olive samples by hydrophilic interaction liquid chromatography (HILIC) separation followed by mass spectrometry detection with tandem mass spectrometry using a triple quadrupole instrument operated in multiple reaction monitoring mode (HILIC-MS/MS) or electrospray time-of-flight mass spectrometry (HILIC-TOFMS). The selected polar pesticides included in the study were: amitrol, cyromazine, diquat, paraquat, mepiquat, trimethylsulfonium (trimesium, glyphosate counterion) and fosetyl aluminium. The simple sample treatment procedure was based on liquid partitioning with methanol. The performance of the sample extraction was evaluated in terms of recovery rates and matrix effects in both olive oil and olives matrices. The results obtained for olive oil were satisfactory while, due to the high complexity of olives, poor recovery rates were obtained for the extraction of diquat, paraquat and amitrol, although with a reasonable precision enabling its use in routine analysis. Similarly, matrix effects were minor in the case of olive oil (ca. 20% suppression average), while significantly higher suppression was observed for olives (30-50% suppression average). The studied approaches were found to be useful for the determination of the pesticides studied in olive oil and olives with limits of quantitation below 5µgkg(-1) in most cases when tandem mass spectrometry was used, thus being in compliance with MRLs set by current EU regulation.

  6. Rapid Detection of Gas Hazards and Leaks with an Atmospheric Sampling, High Resolution, Mass Spectrometer with Low Pumping Requirements Project

    Data.gov (United States)

    National Aeronautics and Space Administration — Miniaturization of mass spectrometers is restricted almost exclusively by the ability of small vacuum pumps to remove gas loads during operation of the instrument....

  7. Determination of anxiolytic veterinary drugs from biological fertilizer blood meal using liquid chromatography high-resolution mass spectrometry.

    Science.gov (United States)

    Choi, Jeong-Heui; Lamshöft, Marc; Zühlke, Sebastian; Park, Jong-Hyouk; Rahman, Md Musfiqur; Abd El-Aty, A M; Spiteller, Michael; Shim, Jae-Han

    2014-06-01

    A liquid environment-friendly agricultural material originating from animal blood, blood meal, was employed to detect anxiolytic veterinary drugs using a combination of liquid-liquid extraction (LLE) and positive electrospray ionization Orbitrap mass spectrometry. Every positive ion of the analytes was consistent with [M+H](+) , and the accurate mass analysis and mass spectral filtration with a 2-ppm mass tolerance window were applied to identify and quantitate the analytes and metabolites. The developed LLE method was validated with the lowest calibrated level, linearity (r(2) ), recovery, repeatability and the within-laboratory reproducibility, which were in the ranges of 0.3-1 µg/L, 0.9963-0.9995, 48.3-117.5%, 1.1-12.6% and 2.3-15.7%, respectively. The LLE method was compared with a solid-phase extraction (SPE) method; however, its recoveries were liquid blood meal samples, and none of the targeted compounds were observed.

  8. High-resolution high-performance liquid chromatography with electrospray ionization mass spectrometry and tandem mass spectrometry characterization of a new isoform of human salivary acidic proline-rich proteins named Roma-Boston Ser22(Phos) → Phe variant

    Science.gov (United States)

    Iavarone, Federica; D’Alessandro, Alfredo; Tian, Na; Cabras, Tiziana; Messana, Irene; Helmerhorst, Eva J.; Oppenheim, Frank G.; Castagnola, Massimo

    2015-01-01

    During a survey of human saliva by a top-down reversed-phase high-performance liquid chromatography with electrospray ionization mass spectrometry approach, two proteins eluting at 27.4 and 28.4 min, with average masses of 15 494 ± 1 and 11 142 ± 1 Da, were detected in a subject from Boston. The Δmass value (4352 Da) of the two proteins was similar to the difference in mass values between intact (150 amino acids, [a.a.]) and truncated acidic proline-rich proteins (aPRPs; 106 a.a.) suggesting an a.a. substitution in the first 106 residues resulting in a strong reduction in polarity, since under the same experimental conditions aPRPs eluted at ~22.5 min (intact) and 23.5 min (truncated forms). Manual inspection of the high-resolution high-performance liquid chromatography with electrospray ionization tandem mass spectra of the truncated isoform showed the replacement of the phosphorylated Ser-22 in PRP-3 with a Phe residue. Inspection of the tandem mass spectra of the intact isoform confirmed the substitution, which is allowed by the code transition TCT→TTT and is in agreement with the dramatic increase in elution time. The isoform was also detected in two other subjects, one from Boston (unrelated to the previous) and one from Rome. For this reason we propose to name this variant PRP-1 (PRP-3) RB (Roma-Boston) Ser22(phos)→Phe. PMID:24771659

  9. Impact of spatial resolution on the modelling of the Greenland ice sheet surface mass balance between 1990–2010, using the regional climate model MAR

    Directory of Open Access Journals (Sweden)

    B. Franco

    2012-02-01

    Full Text Available With the aim to force an ice dynamical model, the Greenland ice sheet (GrIS surface mass balance (SMB was modelled at different spatial resolutions (15–50 km for the period 1990–2010, using the regional climate model MAR (Modèle Atmosphérique Régional forced by the ERA-INTERIM reanalysis. This comparison revealed that (i the inter-annual variability of the SMB components is consistent within the different spatial resolutions investigated, (ii the MAR model simulates heavier precipitation on average over the GrIS with diminishing spatial resolution, and (iii the SMB components (except precipitation can be derived from a simulation at lower resolution with an ''intelligent'' interpolation. This interpolation can also be used to approximate the SMB components over another topography/ice sheet mask of the GrIS. These results are important for the forcing of an ice dynamical model, needed to enable future projections of the GrIS contribution to sea level rise over the coming centuries.

  10. Preschool Teachers' Perceptions about Conflict Resolution, Autonomy, and the Group in Four Countries: United States, Colombia, El Salvador and Taiwan.

    Science.gov (United States)

    Killen, Melanie; Ardila-Rey, Alicia; Barakkatz, Marlene; Wang, Pei-Lin

    2000-01-01

    This study surveyed 160 preschool teachers in 4 countries regarding views of moral and social conflict resolution, autonomy and a group sense, and general aims of preschools. Findings revealed that all hold similar beliefs regarding intervention in children's conflicts and importance of autonomy in the classroom. Additionally, all viewed the…

  11. Wide-Scope Screening Method for Multiclass Veterinary Drug Residues in Fish, Shrimp, and Eel Using Liquid Chromatography-Quadrupole High-Resolution Mass Spectrometry.

    Science.gov (United States)

    Turnipseed, Sherri B; Storey, Joseph M; Lohne, Jack J; Andersen, Wendy C; Burger, Robert; Johnson, Aaron S; Madson, Mark R

    2017-01-13

    A screening method for veterinary drug residues in fish, shrimp, and eel using LC with a high-resolution MS instrument has been developed and validated. The method was optimized for over 70 test compounds representing a variety of veterinary drug classes. Tissues were extracted by vortex mixing with acetonitrile acidified with 2% acetic acid and 0.2% p-toluenesulfonic acid. A centrifuged portion of the extract was passed through a novel solid phase extraction cartridge designed to remove interfering matrix components from tissue extracts. The eluent was then evaporated and reconstituted for analysis. Data were collected with a quadrupole-Orbitrap high-resolution mass spectrometer using both nontargeted and targeted acquisition methods. Residues were detected on the basis of the exact mass of the precursor and a product ion along with isotope pattern and retention time matching. Semiquantitative data analysis compared MS(1) signal to a one-point extracted matrix standard at a target testing level. The test compounds were detected and identified in salmon, tilapia, catfish, shrimp, and eel extracts fortified at the target testing levels. Fish dosed with selected analytes and aquaculture samples previously found to contain residues were also analyzed. The screening method can be expanded to monitor for an additional >260 veterinary drugs on the basis of exact mass measurements and retention times.

  12. Improved resolution of hydrocarbon structures and constitutional isomers in complex mixtures using Gas Chromatography-Vacuum Ultraviolet-Mass Spectrometry (GC-VUV-MS)

    Energy Technology Data Exchange (ETDEWEB)

    Aerosol Dynamics Inc; Aerodyne Research, Inc.,; Tofwerk AG, Thun; Isaacman, Gabriel; Wilson, Kevin R.; Chan, Arthur W. H.; Worton, David R.; Kimmel, Joel R.; Nah, Theodora; Hohaus, Thorsten; Gonin, Marc; Kroll, Jesse H.; Worsnop, Doug R.; Goldstein, Allen H.

    2011-09-13

    Understanding the composition of complex hydrocarbon mixtures is important for environmental studies in a variety of fields, but many prevalent compounds cannot be confidently identified using traditional gas chromatography-mass spectrometry (GC-MS) techniques. This work uses vacuum-ultraviolet (VUV) ionization to elucidate the structures of a traditionally"unresolved complex mixture" by separating components by GC retention time, tR, and mass-to-charge ratio, m/Q, which are used to determine carbon number, NC, and the number of rings and double bonds, NDBE. Constitutional isomers are resolved based on tR, enabling the most complete quantitative analysis to date of structural isomers in an environmentally-relevant hydrocarbon mixture. Unknown compounds are classified in this work by carbon number, degree of saturation, presence of rings, and degree of branching, providing structural constraints. The capabilities of this analysis are explored using diesel fuel, in which constitutional isomer distribution patterns are shown to be reproducible between carbon numbers and follow predictable rules. Nearly half of the aliphatic hydrocarbon mass is shown to be branched, suggesting branching is more important in diesel fuel than previously shown. The classification of unknown hydrocarbons and the resolution of constitutional isomers significantly improves resolution capabilities for any complex hydrocarbon mixture.

  13. [Rapid screening and confirming carcinogenic banned azo colorants in textiles by high performance liquid chromatography-linear ion trap/orbitrap high-resolution mass spectrometry].

    Science.gov (United States)

    Yun, Huan; Liu, Xin; Wang, Jing; Yan, Hua; Cui, Fengyun; Zhang, Zhaohui

    2013-09-01

    A method of high performance liquid chromatography-linear ion trap/orbitrap highresolution mass spectrometry (HPLC-LTP/Orbitrap MS) was ued to screen and confirm-banned azo colorants in textiles rapidly. The analytes were reduced to carcinogenic aromatic amines with sodium dithionite in citrate buffer solution. The reduced solution was extracted bydiatomite, and loadd onto an Acquity UPLC BEH C18 column (50 mm x 2.1 MM. 1.7 microm) with a gradient elution of methanol and 0.1% (v/v) methane acid aqueous solution, and finally detected by linear ion trap/orbitrap high-resolution mass spectrometry in positive ESI mode. In mass spectrometry method, the MS spectrum of high-resolution and the collision induced dissociation (CID) spectrum of data-dependent scan mode were used for screening analysis and conformation, respectively. The calibration curves showed a good linearity in the range of 0.05 -2.00 mg/b, and the correlation coefficients (r) were higher than 0.99. By detecting spiked samples, the limits of quantification were 0.08 mg/kg for all the residues and the recoveries were in the range of 65.5% - 111.5% with the relative standard deviations (RSDs) between 0.87% and 2.49%. The results indicate that the method is simple, rapid, sensitive and suitable for the qualitative and quantitative analysis of carcinogenic aromatic amines in textiles.

  14. Multicomponent mixed dopant optimization for rapid screening of polycyclic aromatic hydrocarbons using ultra high performance liquid chromatography coupled to atmospheric pressure photoionization high-resolution mass spectrometry

    KAUST Repository

    Sioud, Salim

    2012-05-04

    RATIONALE To enhance the ionization efficiencies in atmospheric pressure photoionization mass spectrometry a dopant with favorable ionization energy such as chlorobenzene is typically used. These dopants are typically toxic and difficult to mix with water-soluble organic solvents. In order to achieve a more efficient and less toxic dopant, a multicomponent mixed dopant was explored. METHODS A multicomponent mixed dopant for non-targeted rapid screening of polycyclic aromatic hydrocarbons (PAHs) was developed and optimized using ultra high performance liquid chromatography (UPLC) coupled to atmospheric pressure photoionization high-resolution mass spectrometry. Various single and multicomponent mixed dopants consisting of ethanol, chlorobenzene, bromobenzene, anisole and toluene were evaluated. RESULTS Fourteen out of eighteen PAHs were successfully separated and detected at low pg/μL levels within 5 min with high mass accuracy ≤4 ppm. The optimal mixed multicomponent dopant consisted of ethanol/chlorobenzene/bromobenzene/anisole (98.975:0.1:0.9:0.025, v/v %) and it improved the limit of detection (LOD) by 2- to 10-fold for the tested PAHs compared to those obtained with pure chlorobenzene. CONCLUSIONS A novel multicomponent dopant that contains 99% ethanol and 1% mixture of chlorobenzene, bromobenzene and anisole was found to be an effective dopant mixture to ionize PAHs. The developed UPLC multicomponent dopant assisted atmospheric pressure photoionization high-resolution mass spectrometry offered a rapid non targeted screening method for detecting the PAHs at low pg/;μL levels within a 5 min run time with high mass accuracy a;circ4 ppm. Copyright © 2012 John Wiley & Sons, Ltd.

  15. Pathogenic lineage of Perkinsea associated with mass mortality of frogs across the United States

    Science.gov (United States)

    Isidoro Ayza, Marcos; Lorch, Jeffrey M.; Grear, Daniel; Winzeler, Megan; Calhoun, Daniel L.; Barichivich, William J.

    2017-01-01

    Emerging infectious diseases such as chytridiomycosis and ranavirus infections are important contributors to the worldwide decline of amphibian populations. We reviewed data on 247 anuran mortality events in 43 States of the United States from 1999–2015. Our findings suggest that a severe infectious disease of tadpoles caused by a protist belonging to the phylum Perkinsea might represent the third most common infectious disease of anurans after ranavirus infections and chytridiomycosis. Severe Perkinsea infections (SPI) were systemic and led to multiorganic failure and death. The SPI mortality events affected numerous anuran species and occurred over a broad geographic area, from boreal to subtropical habitats. Livers from all PCR-tested SPI-tadpoles (n = 19) were positive for the Novel Alveolate Group 01 (NAG01) of Perkinsea, while only 2.5% histologically normal tadpole livers tested positive (2/81), suggesting that subclinical infections are uncommon. Phylogenetic analysis demonstrated that SPI is associated with a phylogenetically distinct clade of NAG01 Perkinsea. These data suggest that this virulent Perkinsea clade is an important pathogen of frogs in the United States. Given its association with mortality events and tendency to be overlooked, the potential role of this emerging pathogen in amphibian declines on a broad geographic scale warrants further investigation.

  16. Methylenedioxy designer drugs: mass spectrometric characterization of their glutathione conjugates by means of liquid chromatography-high-resolution mass spectrometry/mass spectrometry and studies on their glutathionyl transferase inhibition potency.

    Science.gov (United States)

    Meyer, Markus R; Richter, Lilian H J; Maurer, Hans H

    2014-04-25

    Methylenedioxy designer drugs of abuse such as 3,4-methylenedioxymethamphetamine (MDMA) can be selectively toxic to serotonergic neurons and glutathione (GSH) adducts have been implicated in its neurotoxicity. The catecholic demethylenyl metabolites of MDMA, 3,4-dihydroxymethamphetamine and 3,4-dihydroxyamphetamine, are metabolically oxidized to the corresponding ortho-quinones, which are highly reactive intermediates. These intermediates can then be conjugated with GSH preventing cellular damage. Furthermore, glutathionyl transferase (GST) activity was described to be irreversibly inhibited by the catechols dopamine, α-methyldopa and their GSH conjugates. Therefore, the aims of the present work were the detection and characterization of GSH conjugates of ten methylenedioxy drugs of abuse and their phase I metabolites as well as to assess their inhibition potency on GST activity. The substrates were incubated using human placental GST with or without preincubation by cytochrome P450 enzymes preparations. GST inhibition was tested using chlorodinitrobenzene GSH conjugation as marker reaction. GSH conjugates were analyzed and characterized using LC-high-resolution-MS/MS. For confirmation of postulated fragmentation patterns, formation of GSH conjugates of selected deuterated analogs (deuterated analogue approach, DAA) of the investigated drugs was explored. For the methylenedioxy amphetamines the following steps could be identified: conjugation of the parent compounds at position 2, 5, 6, of the demethylenyl metabolites at position 2 and 5, and of the further deaminated demethylenyl metabolites at position 2. For the β-keto-phenylalkylamine and pyrrolidinophenone, conjugation of the demethylenyl metabolites and of the deaminated demethylenyl metabolites at position 2 could be identified. The DAA allowed the differentiation of the 2 and 5/6 isomers by confirmation of the postulated mass spectral fragments. Finally, the tested drugs and phase I metabolites showed no

  17. USGS Small-scale Dataset - Global Map: 100-Meter Resolution Elevation of the Conterminous United States 201403 BIL

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — This map layer includes Global Map data showing elevation for the conterminous United States, in meters relative to mean sea level. The data are a modified version...

  18. USGS Small-scale Dataset - 100-Meter Resolution Natural Earth of the Conterminous United States 201308 TIFF

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — This map layer contains a natural-earth image of the conterminous United States. The image is land cover in natural colors combined with shaded relief, which...

  19. Screening of environmental contaminants in honey bee wax comb using gas chromatography-high-resolution time-of-flight mass spectrometry.

    Science.gov (United States)

    Gómez-Ramos, M M; García-Valcárcel, A I; Tadeo, J L; Fernández-Alba, A R; Hernando, M D

    2016-03-01

    This study reports an analytical approach intended to be used for investigation of non-targeted environmental contaminants and to characterize the organic pollution pattern of bee wax comb samples. The method comprises a generic extraction followed by detection with gas chromatography coupled to high-resolution time-of-flight mass spectrometry (GC-TOF-MS), operated in electron impact ionization (EI) mode. The screening approach for the investigation of non-targeted contaminants consisted of initial peak detection by deconvolution and matching the first-stage mass spectra EI-MS(1) with a nominal mass spectral library. To gain further confidence in the structural characterization of the contaminants under investigation, the molecular formula of representative ions (molecular ion when present in the EI spectrum) and, for at least other two fragment ions, was provided for those with an accurate mass scoring (mass error bee wax comb. This approach has allowed the tentative identification of some GC-amenable contaminants belonging to different chemical groups, among them, phthalates and polycyclic aromatic hydrocarbons (PAHs), along with residues of veterinary treatments used in apiculture.

  20. An iodide-adduct high-resolution time-of-flight chemical-ionization mass spectrometer: application to atmospheric inorganic and organic compounds.

    Science.gov (United States)

    Lee, Ben H; Lopez-Hilfiker, Felipe D; Mohr, Claudia; Kurtén, Theo; Worsnop, Douglas R; Thornton, Joel A

    2014-06-03

    A high-resolution time-of-flight chemical-ionization mass spectrometer (HR-ToF-CIMS) using Iodide-adducts has been characterized and deployed in several laboratory and field studies to measure a suite of organic and inorganic atmospheric species. The large negative mass defect of Iodide, combined with soft ionization and the high mass-accuracy (5500) of the time-of-flight mass spectrometer, provides an additional degree of separation and allows for the determination of elemental compositions for the vast majority of detected ions. Laboratory characterization reveals Iodide-adduct ionization generally exhibits increasing sensitivity toward more polar or acidic volatile organic compounds. Simultaneous retrieval of a wide range of mass-to-charge ratios (m/Q from 25 to 625 Th) at a high frequency (>1 Hz) provides a comprehensive view of atmospheric oxidative chemistry, particularly when sampling rapidly evolving plumes from fast moving platforms like an aircraft. We present the sampling protocol, detection limits and observations from the first aircraft deployment for an instrument of this type, which took place aboard the NOAA WP-3D aircraft during the Southeast Nexus (SENEX) 2013 field campaign.

  1. Highly accurate chemical formula prediction tool utilizing high-resolution mass spectra, MS/MS fragmentation, heuristic rules, and isotope pattern matching.

    Science.gov (United States)

    Pluskal, Tomáš; Uehara, Taisuke; Yanagida, Mitsuhiro

    2012-05-15

    Mass spectrometry is commonly applied to qualitatively and quantitatively profile small molecules, such as peptides, metabolites, or lipids. Modern mass spectrometers provide accurate measurements of mass-to-charge ratios of ions, with errors as low as 1 ppm. Even such high mass accuracy, however, is not sufficient to determine the unique chemical formula of each ion, and additional algorithms are necessary. Here we present a universal software tool for predicting chemical formulas from high-resolution mass spectrometry data, developed within the MZmine 2 framework. The tool is based on the use of a combination of heuristic techniques, including MS/MS fragmentation analysis and isotope pattern matching. The performance of the tool was evaluated using a real metabolomic data set obtained with the Orbitrap MS detector. The true formula was correctly determined as the highest-ranking candidate for 79% of the tested compounds. The novel isotope pattern-scoring algorithm outperformed a previously published method in 64% of the tested Orbitrap spectra. The software described in this manuscript is freely available and its source code can be accessed within the MZmine 2 source code repository.

  2. HIghMass - High HI Mass, HI-rich Galaxies at z~0: High-Resolution VLA Imaging of UGC 9037 and UGC 12506

    CERN Document Server

    Hallenbeck, Gregory; Spekkens, Kristine; Haynes, Martha P; Giovanelli, Riccardo; Adams, Elizabeth A K; Brinchmann, Jarle; Chengalur, Jayaram; Hunt, Leslie K; Masters, Karen L; Saintonge, Amélie

    2014-01-01

    We present resolved HI observations of two galaxies, UGC 9037 and UGC 12506, members of a rare subset of galaxies detected by the ALFALFA extragalactic HI survey characterized by high HI mass and high gas fraction for their stellar masses. Both of these galaxies have M$_*>10^{10}$ M$_\\odot$ and M$_\\text{HI}>$ M$_*$, as well as typical star formation rates for their stellar masses. How can such galaxies have avoided consuming their massive gas reservoirs? From gas kinematics, stability, star formation, and dark matter distributions of the two galaxies, we infer two radically different histories. UGC 9037 has high central HI surface density ($>10$ M$_\\odot$ pc$^{-2}$). Its gas at most radii appears to be marginally unstable with non-circular flows across the disk. These properties are consistent with UGC 9037 having recently acquired its gas and that it will soon undergo major star formation. UGC 12506 has low surface densities of HI, and its gas is stable over most of the disk. We predict its gas to be HI-domi...

  3. Characterization of submicron aerosols during a serious pollution month in Beijing (2013 using an aerodyne high-resolution aerosol mass spectrometer

    Directory of Open Access Journals (Sweden)

    J. K. Zhang

    2013-07-01

    Full Text Available In January 2013, Beijing experienced several serious haze events. To achieve a better understanding of the characteristics, sources and processes of aerosols during this month, an Aerodyne High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS was deployed at an urban site between 1 January and 1 February 2013 to obtain the size-resolved chemical composition of non-refractory submicron particles (NR-PM1. During this period, the mean measured NR-PM1 mass concentration was 87.4 μg m-3 and was composed of organics (49.8%, sulfate (21.4%, nitrate (14.6%, ammonium (10.4%, and chloride (3.8%. Moreover, inorganic matter, such as sulfate and nitrate comprised an increasing fraction of the NR-PM1 load as NR-PM1 loading increased, denoting their key roles in particulate pollution during this month. The average size distributions of the species were all dominated by an accumulation mode peaking at approximately 600 nm in vacuum aerodynamic diameter and organics characterized by an additional smaller size (∼200 nm. Elemental analyses showed that the average O/C, H/C, and N/C (molar ratio of organic matter were 0.34, 1.44 and 0.015, respectively, corresponding to an OM/OC ratio (mass ratio of organic matter to organic carbon of 1.60. Positive matrix factorization (PMF analyses of the high-resolution organic mass spectral dataset differentiated the organic aerosol into four components, i.e., oxygenated organic aerosols (OOA, cooking-related (COA, nitrogen-containing (NOA and hydrocarbon-like (HOA, which on average accounted for 40.0, 23.4, 18.1 and 18.5% of the total organic mass, respectively. Back trajectory clustering analyses indicated that the WNW air masses were associated with the highest NR-PM1 pollution during the campaign. Aerosol particles in southern air masses were especially rich in inorganic and oxidized organic species, whereas northern air masses contained a large fraction of primary species.

  4. Dynamics of explosive paroxysms at open andesitic systems: high-resolution mass distribution analyses of 2006 tephra from Tungurahua volcano (Ecuador)

    Science.gov (United States)

    Le Pennec, J.; Eychenne, J.; Ramon, P.; Yepes, H.

    2012-12-01

    Many andesitic volcanoes at subduction plate margins can experience in the course of their evolution periods of sub-continuous eruption during years, decades, or centuries. Such long-lived periods may embrace more or less intense outgassing events, extrusion of viscous lava flows and domes (e.g. Colima in Mexico, Merapi in Indonesia, Arenal in Costa Rica), and explosive activity of uneven intensity (e.g. Semeru in Indonesia, Sakurajima in Japan, Sangay in Ecuador). In addition, strong explosive events of short duration may occur, with potential generation of pyroclastic flows on the flanks and beyond, which can pose significant hazards in populated regions. The origin and dynamics of such violent eruptions remain poorly known and may involve a combination of different factors. Tungurahua volcano, Ecuador, reawaken in 1999 and is an example of such open-system behaviour that experienced a strong and deadly andesitic pyroclastic flow-forming event in August 2006. Inspection of the deposits suggested that the event could have been triggered by magma mixing (silicic pumices in the tephra), magma-water interaction (presence of xenolithic clasts) or deep andesitic magma reinjection (based on mineral chemistry). Here we investigate these options by performing a high-resolution mass budget analysis of the scoria fall deposit. This is achieved by analysing componentry compositions and their mass distribution pattern in the layer, which allow us to document and integrate exponential and power laws mass decay rates over wide areas. The results yield a total mass for the tephra layer of ~2 x 1010kg. The pumice mass fraction is far too small (< 0.4 %) to account for the high explosivity of the 2006 event. Similarly, the xenoclastic mass fraction is small (0.2%) and suggests limited magma-water interaction. Instead, we interpret these xenoclasts as a result of upper conduit erosion at a rate of ~30 cm/hour during the paroxysm. Altogether our results support an explosive event

  5. Mass Balance Assessment for Six Neonicotinoid Insecticides During Conventional Wastewater and Wetland Treatment: Nationwide Reconnaissance in United States Wastewater

    Science.gov (United States)

    2016-01-01

    Occurrence and removal of six high-production high-volume neonicotinoids was investigated in 13 conventional wastewater treatment plants (WWTPs) and one engineered wetland. Flow-weighted daily composites were analyzed by isotope dilution liquid chromatography tandem mass spectrometry, revealing the occurrence of imidacloprid, acetamiprid, and clothianidin at ng/L concentrations in WWTP influent (60.5 ± 40.0; 2.9 ± 1.9; 149.7 ± 289.5, respectively) and effluent (58.5 ± 29.1; 2.3 ± 1.4; 70.2 ± 121.8, respectively). A mass balance showed insignificant removal of imidacloprid (p = 0.09, CI = 95%) and limited removal of the sum of acetamiprid and its degradate, acetamiprid-N-desmethyl (18 ± 4%, p = 0.01, CI = 95%). Clothianidin was found only intermittently, whereas thiamethoxam, thiacloprid, and dinotefuran were never detected. In the wetland, no removal of imidacloprid or acetamiprid was observed. Extrapolation of data from 13 WWTPs to the nation as a whole suggests annual discharges on the order of 1000–3400 kg/y of imidacloprid contained in treated effluent to surface waters nationwide. This first mass balance and first United States nationwide wastewater reconnaissance identified imidacloprid, acetamiprid, and clothianidin as recalcitrant sewage constituents that persist through wastewater treatment to enter water bodies at significant loadings, potentially harmful to sensitive aquatic invertebrates. PMID:27196423

  6. Environmental screening of acidic compounds based on capillary zone electrophoresis/laser-induced fluorescence detection with identification by gas chromatography/mass spectrometry and gas chromatography/high-resolution mass spectrometry.

    Science.gov (United States)

    Brumley, W C; Grange, A H; Kelliher, V; Patterson, D B; Montcalm, A; Glassman, J; Farley, J W

    2000-01-01

    This paper describes the application of capillary zone electrophoresis/laser-induced fluorescence detection (CZE/LIF) to the discovery of acidic compounds in environmental matrixes or the screening of extracts for acidic components. Published studies indicate that coal-derived materials contain a significant fraction of acidic compounds relative to materials derived from petroleum and shales. Such compounds may be useful as marker compounds for site assessment and source apportionment issues, and their identification may be important in toxicological and other health issues. We used deep-UV light from the frequency-doubled Ar ion laser at 244 and 257 nm to study extracts of samples. The CZE/LIF technique possesses good sensitivity and therefore overcomes one of the limitations of CZE with UV detection. The present work depends on high pressure/temperature solvent extraction of polynuclear aromatic hydrocarbon (PNA)-contaminated soil, followed by separation using CZE. The anionic analytes were separated by using borate or phosphate buffer (pH 9.2-12.3) after a chemical class separation. Samples were also characterized by gas chromatography/mass spectrometry (GC/MS) using full scans at low resolution, and elemental compositions were determined unequivocally by GC/high-resolution MS (GC/HRMS) using mass peak profiling (MPP). The similarity of low-resolution electron ionization mass spectra for a standard, 1-hydroxypyrene, and for a series of compounds in a contaminated-soil extract suggested that several types of phenolic and hydroxy-PNAs were present, including hydroxylated derivatives of fluorenes, fluoranthenes, and pyrenes. GC/HRMS using MPP confirmed the elemental compositions of the hydroxyfluorenes and hydroxypyrenes (and presumably hydroxyfluoranthenes) as [C13H10O] and [C16H10O], respectively. A new version of the MPP software was written for the Finnigan-MAT 900S-Trap and was similar to that developed previously for the VG 250SE. Inclusion of a calibration

  7. The recent prevalence of Osteoporosis and low bone mass in the United States based on bone mineral density at the Femoral Neck or Lumbar Spine

    Science.gov (United States)

    The goal of our study was to estimate the prevalence of osteoporosis and low bone mass based on bone mineral density (BMD) at the femoral neck and the lumbar spine in adults 50 years and older in the United States (US). We applied prevalence estimates of osteoporosis or low bone mass at the femoral ...

  8. The Scales of Time, Length, Mass, Energy, and Other Fundamental Physical Quantities in the Atomic World and the Use of Atomic Units in Quantum Mechanical Calculations

    Science.gov (United States)

    Teo, Boon K.; Li, Wai-Kee

    2011-01-01

    This article is divided into two parts. In the first part, the atomic unit (au) system is introduced and the scales of time, space (length), and speed, as well as those of mass and energy, in the atomic world are discussed. In the second part, the utility of atomic units in quantum mechanical and spectroscopic calculations is illustrated with…

  9. Ozone-induced dissociation on a traveling wave high-resolution mass spectrometer for determination of double-bond position in lipids.

    Science.gov (United States)

    Vu, Ngoc; Brown, Jeffery; Giles, Kevin; Zhang, Qibin

    2017-09-15

    The position of C=C within fatty acyl chains affects the biological function of lipids. Ozone-induced dissociation mass spectrometry (OzID-MS) has great potential in determination of lipid double-bond position, but has generally been implemented on low-resolution ion trap mass spectrometers. In addition, most of the OzID-MS experiments carried out so far were focused on the sodiated adducts of lipids; fragmentation of the most commonly observed protonated ions generated in LC/MS-based lipidomics workflow has been less explored. Ozone generated in line from an ozone generator was connected to the trap and transfer gas supply line of a Synapt G2 high-resolution mass spectrometer. Protonated ions of different phosphatidylcholines (PC) were generated by electrospray ionization through direct infusion. Different parameters, including traveling wave height and velocity, trap entrance and DC potential, were adjusted to maximize the OzID efficiency. sn-positional isomers and cis/trans isomers of lipids were compared for their reactivity with ozone. Traveling wave height and velocity were tuned to prolong the encounter time between lipid ions and ozone, and resulted in improved OzID efficiency, as did increasing trapping region DC and entrance potential. Under optimized settings, at least 1000 times enhancement in OzID efficiency was achieved compared to that under default settings for monounsaturated PC standards. Monounsaturated C=C in the sn-2 PC isomer reacted faster with ozone than the sn-1 isomer. Similarly, the C=C in trans PC reacted faster than in cis PC. This is the first implementation of OzID in the trap and transfer region of a traveling wave enabled high-resolution mass spectrometer. The OzID reaction efficiency is significantly improved by slowing down ions in the trap region for their prolonged interaction with ozone. This will facilitate application of high-resolution OzID-MS in lipidomics. Copyright © 2017 John Wiley & Sons, Ltd.

  10. Impurity profiling of liothyronine sodium by means of reversed phase HPLC, high resolution mass spectrometry, on-line H/D exchange and UV/Vis absorption.

    Science.gov (United States)

    Ruggenthaler, M; Grass, J; Schuh, W; Huber, C G; Reischl, R J

    2017-09-05

    For the first time, a comprehensive investigation of the impurity profile of the synthetic thyroid API (active pharmaceutical ingredient) liothyronine sodium (LT3Na) was performed by using reversed phase HPLC and advanced structural elucidation techniques including high resolution tandem mass spectrometry (HRMS/MS) and on-line hydrogen-deuterium (H/D) exchange. Overall, 39 compounds were characterized and 25 of these related substances were previously unknown to literature. The impurity classification system recently developed for the closely related API levothyroxine sodium (LT4Na) could be applied to the newly characterized liothyronine sodium impurities resulting in a wholistic thyroid API impurity classification system. Furthermore, the mass-spectrometric CID-fragmentation of specific related substances was discussed and rationalized by detailed fragmentation pathways. Moreover, the UV/Vis absorption characteristics of the API and selected impurities were investigated to corroborate chemical structure assignments derived from MS data. Copyright © 2017 Elsevier B.V. All rights reserved.

  11. LYMPHOCYTIC HYPOPHYSITIS: A RARE AUTOIMMUNE DISORDER PRESENT IN A LARGE SUPRA SELLAR MASS HAVING COMPLETE RESOLUTION WITH STEROIDS.

    Science.gov (United States)

    Rafiq, Mirza Faisal Ahmed; Farooq, Umar; Khan, Adil Aziz; Noor-ul-Ain

    2015-01-01

    Significant proportion of sellar masses is seen in clinical practice. They range from most common pituitary adenomas to rare inflammatory lesions. Presentation can vary and depends if it secretes any hormone or imparts a pressure effect upon the surrounding vital structures. Radiological imaging coupled with histopathology is important tools of diagnosis. Management options depend upon type of disease.

  12. Elucidation and identification of amino acid containing membrane lipids using liquid chromatography/high-resolution mass spectrometry

    NARCIS (Netherlands)

    Moore, E.K.; Hopmans, E.C.; Rijpstra, W.I.C.; Villanueva, L.; Sinninghe Damsté, J.S.

    2016-01-01

    RATIONALE: Intact polar lipids (IPLs) are the building blocks of cell membranes, and amino acid containing IPLs havebeen observed to be involved in response to changing environmental conditions in various species of bacteri a. High-performance liquid chromatography/mass spectrometry (HPLC/MS) has be

  13. Accurate and precise 40Ar/39Ar dating by high-resolution, multi-collection, mass spectrometry

    DEFF Research Database (Denmark)

    Storey, Michael; Rivera, Tiffany; Flude, Stephanie

    -Instruments multi-collector Noblesse noble gas mass spectrometer configured with a faraday detector and three ion-counting electron multipliers. The instrument has the capability to measure several noble gas isotopes simultaneously and to change measurement configurations instantaneously by the use of QUAD lenses...

  14. Chemical composition, sources, and processes of urban aerosols during summertime in northwest China: insights from high-resolution aerosol mass spectrometry

    Science.gov (United States)

    Xu, J.; Zhang, Q.; Chen, M.; Ge, X.; Ren, J.; Qin, D.

    2014-12-01

    An Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was deployed along with a scanning mobility particle sizer (SMPS) and a multi-angle absorption photometer (MAAP) to measure the temporal variations of the mass loading, chemical composition, and size distribution of submicron particulate matter (PM1) in Lanzhou, northwest China, during 11 July-7 August 2012. The average (PM1 mass concentration including non-refractory (PM1 (NR-(PM1) measured by HR-ToF-AMS and black carbon (BC) measured by MAAP during this study was 24.5 μg m-3 (ranging from 0.86 to 105 μg m-3), with a mean composition consisting of 47% organics, 16% sulfate, 12% BC, 11% ammonium, 10% nitrate, and 4% chloride. Organic aerosol (OA) on average consisted of 70% carbon, 21% oxygen, 8% hydrogen, and 1% nitrogen, with the average oxygen-to-carbon ratio (O / C) of 0.33 and organic mass-to-carbon ratio (OM / OC) of 1.58. Positive matrix factorization (PMF) of the high-resolution organic mass spectra identified four distinct factors which represent, respectively, two primary OA (POA) emission sources (traffic and food cooking) and two secondary OA (SOA) types - a fresher, semi-volatile oxygenated OA (SV-OOA) and a more aged, low-volatility oxygenated OA (LV-OOA). Traffic-related hydrocarbon-like OA (HOA) and BC displayed distinct diurnal patterns, both with peak at ~ 07:00-11:00 (BJT: UTC +8), corresponding to the morning rush hours, while cooking-emission related OA (COA) peaked during three meal periods. The diurnal profiles of sulfate and LV-OOA displayed a broad peak between ~ 07:00 and 15:00, while those of nitrate, ammonium, and SV-OOA showed a narrower peak between ~ 08:00-13:00. The later morning and early afternoon maximum in the diurnal profiles of secondary aerosol species was likely caused by downward mixing of pollutants aloft, which were likely produced in the residual layer decoupled from the boundary layer during nighttime. The mass spectrum of SV-OOA was

  15. Allergy vaccines: a need for standardisation in mass units of major allergen.

    Science.gov (United States)

    van Ree, R; Dorpema, J W; Vieths, S

    2005-09-01

    Treatment of respiratory allergies can be performed with allergen-specific immunotherapy using allergen extracts. These products are biologicals with an extremely complex and variable composition. Only a few components are of major importance for the disease, the so-called major allergens. At present, standardisation of allergen extracts is dominated by techniques that aim at establishing their overall IgE-binding potencies using pooled sera of allergic patients. Each company in the market uses its own type of units to express potencies, thus hampering comparability. Another disadvantage is that the major allergen composition is not determined. Most companies have introduced assays for the measurement of major allergens in their quality control systems, but these data are not yet used for labelling purposes. The need to include major allergen content in standardisation protocols is now widely accepted. To support future labelling on the basis of major allergen content the European Union has funded the multidisciplinary multicentre project CREATE. This project aims at developing international certified references for the most important major respiratory allergens and at evaluating the performance of available ELISA for their measurement. The project will facilitate expression of potencies by active ingredient (major allergen) content and will allow direct comparison of competitor products.

  16. Conformational ordering of biomolecules in the gas phase: nitrogen collision cross sections measured on a prototype high resolution drift tube ion mobility-mass spectrometer.

    Science.gov (United States)

    May, Jody C; Goodwin, Cody R; Lareau, Nichole M; Leaptrot, Katrina L; Morris, Caleb B; Kurulugama, Ruwan T; Mordehai, Alex; Klein, Christian; Barry, William; Darland, Ed; Overney, Gregor; Imatani, Kenneth; Stafford, George C; Fjeldsted, John C; McLean, John A

    2014-02-18

    Ion mobility-mass spectrometry measurements which describe the gas-phase scaling of molecular size and mass are of both fundamental and pragmatic utility. Fundamentally, such measurements expand our understanding of intrinsic intramolecular folding forces in the absence of solvent. Practically, reproducible transport properties, such as gas-phase collision cross-section (CCS), are analytically useful metrics for identification and characterization purposes. Here, we report 594 CCS values obtained in nitrogen drift gas on an electrostatic drift tube ion mobility-mass spectrometry (IM-MS) instrument. The instrument platform is a newly developed prototype incorporating a uniform-field drift tube bracketed by electrodynamic ion funnels and coupled to a high resolution quadrupole time-of-flight mass spectrometer. The CCS values reported here are of high experimental precision (±0.5% or better) and represent four chemically distinct classes of molecules (quaternary ammonium salts, lipids, peptides, and carbohydrates), which enables structural comparisons to be made between molecules of different chemical compositions for the rapid "omni-omic" characterization of complex biological samples. Comparisons made between helium and nitrogen-derived CCS measurements demonstrate that nitrogen CCS values are systematically larger than helium values; however, general separation trends between chemical classes are retained regardless of the drift gas. These results underscore that, for the highest CCS accuracy, care must be exercised when utilizing helium-derived CCS values to calibrate measurements obtained in nitrogen, as is the common practice in the field.

  17. The stellar mass - size relation for cluster galaxies at z=1 with high angular resolution from the Gemini/GeMS multi-conjugate adaptive optics system

    CERN Document Server

    Sweet, Sarah M; Glazebrook, Karl; Rigaut, Francois; Carrasco, Eleazar R; Brodwin, Mark; Baylliss, Matthew; Stalder, Brian; Abraham, Roberto; McGregor, Peter

    2016-01-01

    We present the stellar mass - size relation for 49 galaxies within the $z$ = 1.067 cluster SPT-CL J0546$-$5345, with FWHM $\\sim$80-120 mas $K_{\\mathrm s}$-band data from the Gemini multi-conjugate adaptive optics system (GeMS/GSAOI). This is the first such measurement in a cluster environment, performed at sub-kpc resolution at rest-frame wavelengths dominated by the light of the underlying old stellar populations. The observed stellar mass - size relation is offset from the local relation by 0.21 dex, corresponding to a size evolution proportional to $(1+z)^{-1.25}$, consistent with the literature. The slope of the stellar mass - size relation $\\beta$ = 0.74 $\\pm$ 0.06, consistent with the local relation. The absence of slope evolution indicates that the amount of size growth is constant with stellar mass. This suggests that galaxies in massive clusters such as SPT-CL J0546$-$5345 grow via processes that increase the size without significant morphological interference, such as minor mergers and/or adiabatic ...

  18. [Screening and confirmation of 24 hormones in cosmetics by ultra high performance liquid chromatography-linear ion trap/orbitrap high resolution mass spectrometry].

    Science.gov (United States)

    Li, Zhaoyong; Wang, Fengmei; Niu, Zengyuan; Luo, Xin; Zhang, Gang; Chen, Junhui

    2014-05-01

    A method of ultra high performance liquid chromatography-linear ion trap/orbitrap high resolution mass spectrometry (UPLC-LTQ/Orbitrap MS) was established to screen and confirm 24 hormones in cosmetics. Various cosmetic samples were extracted with methanol. The extract was loaded onto a Waters ACQUITY UPLC BEH C18 column (50 mm x 2.1 mm, 1.7 microm) using a gradient elution of acetonitrile/water containing 0.1% (v/v) formic acid for the separation. The accurate mass of quasi-molecular ion was acquired by full scanning of electrostatic field orbitrap. The rapid screening was carried out by the accurate mass of quasi-molecular ion. The confirmation analysis for targeted compounds was performed with the retention time and qualitative fragments obtained by data dependent scan mode. Under the optimal conditions, the 24 hormones were routinely detected with mass accuracy error below 3 x 10(-6) (3 ppm), and good linearities were obtained in their respective linear ranges with correlation coefficients higher than 0.99. The LODs (S/N = 3) of the 24 compounds were hormones in 50 cosmetic samples. The results demonstrate that the method is a useful tool for the rapid screening and identification of the hormones in cosmetics.

  19. Measurement of Surface Displacement and Deformation of Mass Movements Using Least Squares Matching of Repeat High Resolution Satellite and Aerial Images

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    Misganu Debella-Gilo

    2012-01-01

    Full Text Available Displacement and deformation are fundamental measures of Earth surface mass movements such as glacier flow, rockglacier creep and rockslides. Ground-based methods of monitoring such mass movements can be costly, time consuming and limited in spatial and temporal coverage. Remote sensing techniques, here matching of repeat optical images, are increasingly used to obtain displacement and deformation fields. Strain rates are usually computed in a post-processing step based on the gradients of the measured velocity field. This study explores the potential of automatically and directly computing velocity, rotation and strain rates on Earth surface mass movements simultaneously from the matching positions and the parameters of the geometric transformation models using the least squares matching (LSM approach. The procedures are exemplified using bi-temporal high resolution satellite and aerial images of glacier flow, rockglacier creep and land sliding. The results show that LSM matches the images and computes longitudinal strain rates, transverse strain rates and shear strain rates reliably with mean absolute deviations in the order of 10−4 (one level of significance below the measured values as evaluated on stable grounds. The LSM also improves the accuracy of displacement estimation of the pixel-precision normalized cross-correlation by over 90% under ideal (simulated circumstances and by about 25% for real multi-temporal images of mass movements.

  20. Target analysis and retrospective screening of veterinary drugs, ergot alkaloids, plant toxins and other undesirable substances in feed using liquid chromatography-high resolution mass spectrometry.

    Science.gov (United States)

    León, Nuria; Pastor, Agustín; Yusà, Vicent

    2016-01-01

    A comprehensive strategy combining a quantitative method for 77 banned veterinary drugs, mycotoxins, ergot alkaloids and plant toxins, and a post-target screening for 425 substances including pesticides and environmental contaminants in feed were developed using a QuEChERS-based extraction and an ultra-high performance liquid chromatography coupled to high-resolution mass spectrometry (UHPLC-HRMS). The quantitative method was validated after previous statistical optimisation of the main parameters governing ionisation, and presented recoveries ranging, in general, from 80 to 120%, with a precision in terms of Relative Standard Deviation (RSD) lower than 20%. The full-scan accurate mass data were acquired with a resolving power of 50000 FWHM and a mass accuracy lower than 5ppm. The method LOQ was lower than 12.5µgkg(-1) for the majority of the veterinary drugs and plant toxins and 20µgkg(-1) for ergot alkaloids. For post-target screening a customised theoretical database including the exact mass, the polarity of acquisition and the expected adducts was built and used for post-run retrospective screening. The analytical strategy was applied to 32 feed samples collected from farms of the Valencia Region (Spain). Florfenicol, zearalenone and atropine were identified and quantified at concentrations around 10µgkg(-1). In the post-target screening of the real samples, Sulfadiazine, Thrimetoprin and Pirimiphosmethyl were tentatively identified.

  1. Direct analysis in real time - high resolution mass spectrometry (DART-HRMS): a high throughput strategy for identification and quantification of anabolic steroid esters.

    Science.gov (United States)

    Doué, Mickael; Dervilly-Pinel, Gaud; Pouponneau, Karinne; Monteau, Fabrice; Le Bizec, Bruno

    2015-07-01

    High throughput screening is essential for doping, forensic, and food safety laboratories. While hyphenated chromatography-mass spectrometry (MS) remains the approach of choice, recent ambient MS techniques, such as direct analysis in real time (DART), offer more rapid and more versatile strategies and thus gain in popularity. In this study, the potential of DART hyphenated with Orbitrap-MS for fast identification and quantification of 21 anabolic steroid esters has been evaluated. Direct analysis in high resolution scan mode allowed steroid esters screening by accurate mass measurement (Resolution = 60 000 and mass error  0.99), dynamic range (from 1 to 1000 ng mL(-1) ), bias (<10%), sensitivity (1 ng mL(-1) ), repeatability and reproducibility (RSD < 20%) were evaluated as similar to those obtained with hyphenated chromatography-mass spectrometry techniques. This innovative high throughput approach was successfully applied for the characterization of oily commercial preparations, and thus fits the needs of the competent authorities in the fight against forbidden or counterfeited substances.

  2. Simulating the climatic mass balance of Svalbard glaciers from 2003 to 2013 with a high-resolution coupled atmosphere-glacier model

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    K. S. Aas

    2015-10-01

    Full Text Available In this study we simulate the climatic mass balance of Svalbard glaciers with a coupled atmosphere-glacier model with 3 km grid spacing, from September 2003 to September 2013. We find a mean specific net mass balance of −167 mm w.e. yr−1, corresponding to a mean annual mass loss of about 5.7 Gt, with large interannual variability. Our results are compared with a comprehensive set of mass balance, meteorological and satellite measurements. Model temperature biases of 0.17 and −1.9 °C are found at two glacier automatic weather station sites. Simulated climatic mass balance is mostly within about 0.1 m w.e. yr−1 of stake measurements, and simulated winter accumulation at the Austfonna ice cap shows mean absolute errors of 0.05 and 0.06 m w.e. yr−1 when compared to radar-derived values for the selected years 2004 and 2006. Comparison of surface height changes from 2003 to 2008 from model, and satellite altimetry reveals good agreement in both mean values and regional differences. The largest deviations from observations are found for winter accumulation at Hansbreen (up to around 1 m w.e. yr−1, a site where sub-grid topography and wind redistribution of snow are important factors. Comparison with simulations using a 9 km grid spacing reveal considerable differences on regional and local scales. In addition, the 3 km grid spacing allows for a much more detailed comparison with observations than what is possible with a 9 km grid spacing. Further decreasing the grid spacing to 1 km appears to be less significant, although in general precipitation amounts increase with resolution. Altogether, the model compares well with observations and offers possibilities for studying glacier climatic mass balance on Svalbard both historically as well as based on climate projections.

  3. Characterization of lemon (Citrus limon) polar extract by liquid chromatography-tandem mass spectrometry in high resolution mode.

    Science.gov (United States)

    Ledesma-Escobar, C A; Priego-Capote, F; Luque de Castro, M D

    2015-11-01

    Eighty four metabolites (32 flavonoids, 15 amino acids, nine carboxylic acids, six coumarins, six sugars, five phenolic acids and 11 unclassified compounds) have been tentatively identified in a polar extract from lemon, without reference standards, based on their liquid chromatography-quadrupole-time-of-flight MS/MS spectra and the comparison with databases. Despite information in databases for some families of plant compounds is poor, tentative identification based on MS/MS information (mass of the precursor ion and their fragments, together with neutral mass loss) was possible with the help of known fragmentation patterns for the given families of compounds. Both positive and negative ionization modes and at least two collision energies were always applied to obtain as much information as possible from each molecular entity, thus helping for identification. As the tentatively identified metabolites are the same regardless of the organism they belong, their fragmentation patterns are useful for identification with independence of the sample nature.

  4. Analytical Characterization of two new related impurities of Diltiazem by High Resolution Mass spectrometry and NMR techniques096

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    Jagadeesh Narkedimilli

    2015-09-01

    Full Text Available Diltiazem (DTZ is an optically active calcium channel blocker having a benzodiazepine structure. Two impurities (referred as DTZ-I and DTZ-II were detected with area percentages ranging from 0.1% to 0.15% during the impurity profile study of Diltiazem hydrochloride drug substance. A simple isocratic high performance liquid chromatographic method (HPLC and liquid chromatography–mass spectrometry (LC–MS were used for the detection. The impurities were isolated by preparative column chromatography. Analytical information from nuclear magnetic resonance and mass spectral data of the potential impurities revealed their structures as 2-(4-methoxyphenyl-5-methyl-4-oxo-2,3,4,5-tetrahydrobenzo[b][1,4]thiazepin-3-yl acetate (DTZ-I and 2-(4-methoxyphenyl-4-oxo-5-vinyl-2,3,4,5-tetrahydrobenzo[b][1,4]thiazepin-3-yl acetate (DTZ-II. Impurity identification, isolation and structure elucidation were discussed.

  5. Measuring Distributional Inequality: Relative Body Mass Index Distributions by Gender, Race/Ethnicity, and Education, United States (1999–2006

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    Brian C. Houle

    2010-01-01

    Full Text Available Few studies consider obesity inequalities as a distributional property. This study uses relative distribution methods to explore inequalities in body mass index (BMI; kg/m2. Data from 1999–2006 from the National Health and Nutrition Examination Survey were used to compare BMI distributions by gender, Black/White race, and education subgroups in the United States. For men, comparisons between Whites and Blacks show a polarized relative distribution, with more Black men at increased risk of over or underweight. Comparisons by education (overall and within race/ethnic groups effects also show a polarized relative distribution, with more cases of the least educated men at the upper and lower tails of the BMI distribution. For women, Blacks have a greater probability of high BMI values largely due to a right-shifted BMI distribution relative to White women. Women with less education also have a BMI distribution shifted to the right compared to the most educated women.

  6. Estimating mass-wasting processes in active earth slides – earth flows with time-series of High-Resolution DEMs from photogrammetry and airborne LiDAR

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    A. Corsini

    2009-03-01

    Full Text Available This paper deals with the use of time-series of High-Resolution Digital Elevation Models (HR DEMs obtained from photogrammetry and airborne LiDAR coupled with aerial photos, to analyse the magnitude of recently reactivated large scale earth slides – earth flows located in the northern Apennines of Italy. The landslides underwent complete reactivation between 2001 and 2006, causing civil protection emergencies. With the final aim to support hazard assessment and the planning of mitigation measures, high-resolution DEMs are used to identify, quantify and visualize depletion and accumulation in the slope resulting from the reactivation of the mass movements. This information allows to quantify mass wasting, i.e. the amount of landslide material that is wasted during reactivation events due to stream erosion along the slope and at its bottom, resulting in sediment discharge into the local fluvial system, and to assess the total volumetric magnitude of the events. By quantifying and visualising elevation changes at the slope scale, results are also a valuable support for the comprehension of geomorphological processes acting behind the evolution of the analysed landslides.

  7. Qualitative and quantitative determination of YiXinShu Tablet using ultra high performance liquid chromatography with Q Exactive hybrid quadrupole orbitrap high-resolution accurate mass spectrometry.

    Science.gov (United States)

    Sun, Zhi; Li, Zhuolun; Zuo, Lihua; Wang, Zhenhui; Zhou, Lin; Shi, Yingying; Kang, Jian; Zhu, Zhenfeng; Zhang, Xiaojian

    2017-08-24

    To clarify and quantify the chemical profile of YiXinShu Tablet rapidly, a feasible and accurate strategy was developed by applying ultra high performance liquid chromatography with Q Exactive hybrid quadrupole orbitrap high-resolution accurate mass spectrometry. A total of 105 components were identified, including 25 phenanthraquinones, 11 lactones, 19 lignans, 24 acids and 26 other compounds. Among them, 26 major compounds were unambiguously detected by comparing with reference standards. And 19 of these compounds in three batches of YiXinShu Tablet were selected for quantitative determination. (Z)-Ligustilide, salvianic acid A, salvianolic acid A, salvianolic acid B and rosmarinic acid were abundant in these three batches with contents over 1.000 mg/g. The established analysis methods were examined to be accurate and feasible. The results show that the ultra high performance liquid chromatography with Q Exactive hybrid quadrupole orbitrap high-resolution accurate mass spectrometry method has a powerful qualitative ability and promising quantitative application. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

  8. Comparative Analysis of the Volatile Components of Agrimonia eupatoria from Leaves and Roots by Gas Chromatography-Mass Spectrometry and Multivariate Curve Resolution

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    Xiao-Liang Feng

    2013-01-01

    Full Text Available Gas chromatography-mass spectrometry and multivariate curve resolution were applied to the differential analysis of the volatile components in Agrimonia eupatoria specimens from different plant parts. After extracted with water distillation method, the volatile components in Agrimonia eupatoria from leaves and roots were detected by GC-MS. Then the qualitative and quantitative analysis of the volatile components in the main root of Agrimonia eupatoria was completed with the help of subwindow factor analysis resolving two-dimensional original data into mass spectra and chromatograms. 68 of 87 separated constituents in the total ion chromatogram of the volatile components were identified and quantified, accounting for about 87.03% of the total content. Then, the common peaks in leaf were extracted with orthogonal projection resolution method. Among the components determined, there were 52 components coexisting in the studied samples although the relative content of each component showed difference to some extent. The results showed a fair consistency in their GC-MS fingerprint. It was the first time to apply orthogonal projection method to compare different plant parts of Agrimonia eupatoria, and it reduced the burden of qualitative analysis as well as the subjectivity. The obtained results proved the combined approach powerful for the analysis of complex Agrimonia eupatoria samples. The developed method can be used to further study and quality control of Agrimonia eupatoria.