WorldWideScience

Sample records for ptr-ms emission ratios

  1. Determination of material emission signatures by PTR-MS and their correlations with odor assessments by human subjects

    DEFF Research Database (Denmark)

    K H, Han; J S, Zhang; Wargocki, Pawel

    2010-01-01

    by human subjects. VOC emissions from each material were measured in a 50-l small-scale chamber. Chamber air was sampled by PTR-MS to determine emission signatures. Sorbent tube sampling and TD-GC/MS analysis were also performed to identify the major VOCs emitted and to compare the resulting data...... VOC odor indices was used to represent the emission level measured by PTR-MS.......The objectives of this study were to determine volatile organic compound (VOC) emission signatures of nine typical building materials by using proton transfer reaction-mass spectrometry (PTR-MS) and to explore the correlation between the PTR-MS measurements and the measurements of acceptability...

  2. PTR-MS as a technique for investigating stress induced emission of biogenic VOCS

    International Nuclear Information System (INIS)

    Beauchamp, J.; Hansel, A.; Wisthaler, A.; Kleist, E.; Miebach, M.; Weller, U.; Wildt, J.

    2004-01-01

    Proton-transfer-reaction mass spectrometry (PTR-MS) was used in conjunction with two GC-MS systems to investigate stress induced emissions of volatile organic compounds (VOCs) from plants. Experiments were performed in the laboratory under well defined conditions and VOC emissions were induced by ozone exposure at variable concentrations and for different durations. Tobacco (Nicotiana tabaccum cv. Bel W3) plants were used as the investigated species. This investigation demonstrated the ability of PTR-MS to provide excellent high time-resolution on-line measurements of the relevant species. The combination of the PTR-MS instrument with the two GC-MS systems (which enabled accurate compound identification) allowed for detailed investigation of the dynamics of the plants' responses to ozone stress. VOCs measured included methanol, C6- alcohols and aldehydes, methyl salicylate and sesquiterpenes. Results indicate that the temporal stress response of plants depend on the amount of stress encountered by the plant. Measurement technique and experimental results will be presented. (author)

  3. The Tropical Forest and Fire Emissions Experiment: method evaluation of volatile organic compound emissions measured by PTR-MS, FTIR, and GC from tropical biomass burning

    Directory of Open Access Journals (Sweden)

    T. G. Karl

    2007-11-01

    Full Text Available Volatile Organic Compound (VOC emissions from fires in tropical forest fuels were quantified using Proton-Transfer-Reaction Mass Spectrometry (PTRMS, Fourier Transform Infrared Spectroscopy (FTIR and gas chromatography (GC coupled to PTRMS (GC-PTR-MS. We investigated VOC emissions from 19 controlled laboratory fires at the USFS (United States Forest Service Fire Sciences Laboratory and 16 fires during an intensive airborne field campaign during the peak of the burning season in Brazil in 2004. The VOC emissions were dominated by oxygenated VOCs (OVOC (OVOC/NMHC ~4:1, NMHC: non-methane hydrocarbons The specificity of the PTR-MS instrument, which measures the mass to charge ratio of VOCs ionized by H3O+ ions, was validated by gas chromatography and by intercomparing in-situ measurements with those obtained from an open path FTIR instrument. Emission ratios for methyl vinyl ketone, methacrolein, crotonaldehyde, acrylonitrile and pyrrole were measured in the field for the first time. Our measurements show a higher contribution of OVOCs than previously assumed for modeling purposes. Comparison of fresh (<15 min and aged (>1 h–1 d smoke suggests altered emission ratios due to gas phase chemistry for acetone but not for acetaldehyde and methanol. Emission ratios for numerous, important, reactive VOCs with respect to acetonitrile (a biomass burning tracer are presented.

  4. A comparison of GC-FID and PTR-MS toluene measurements in ambient air under conditions of enhanced monoterpene loading

    Directory of Open Access Journals (Sweden)

    J. L. Ambrose

    2010-07-01

    Full Text Available Toluene was measured using both a gas chromatographic system (GC, with a flame ionization detector (FID, and a proton transfer reaction-mass spectrometer (PTR-MS at the AIRMAP atmospheric monitoring station Thompson Farm (THF in rural Durham, NH during the summer of 2004. Simultaneous measurements of monoterpenes, including α- and β-pinene, camphene, Δ 3-carene, and d-limonene, by GC-FID demonstrated large enhancements in monoterpene mixing ratios relative to toluene, with median and maximum enhancement ratios of ~2 and ~30, respectively. A detailed comparison between the GC-FID and PTR-MS toluene measurements was conducted to test the specificity of PTR-MS for atmospheric toluene measurements under conditions often dominated by biogenic emissions. We derived quantitative estimates of potential interferences in the PTR-MS toluene measurements related to sampling and analysis of monoterpenes, including fragmentation of the monoterpenes and some of their primary carbonyl oxidation products via reactions with H3O+, O2+ and NO+ in the PTR-MS drift tube. The PTR-MS and GC-FID toluene measurements were in good quantitative agreement and the two systems tracked one another well from the instrumental limits of detection to maximum mixing ratios of ~0.5 ppbv. A correlation plot of the PTR-MS versus GC-FID toluene measurements was described by the least squares regression equation y=(1.13± 0.02x−(0.008±0.003 ppbv, suggesting a small ~13% positive bias in the PTR-MS measurements. The bias corresponded with a ~0.055 ppbv difference at the highest measured toluene level. The two systems agreed quantitatively within the combined 1σ measurement precisions for 60% of the measurements. Discrepancies in the measured mixing ratios were not well correlated with enhancements in the monoterpenes. Better quantitative agreement between the two systems was obtained by

  5. PTR-MS in environmental research: biogenic VOCs

    International Nuclear Information System (INIS)

    Beauchamp, J.; Grabmer, W.; Graus, M.; Wisthaler, A.; Hansel, A.

    2004-01-01

    Proton-transfer-reaction mass spectrometry (PTR-MS) is a chemical ionization mass spectrometry technique that allows for on-line measurements of volatile organic compounds (VOCs) at pptV levels. This well established analytical tool has been used in a broad variety of research, including the investigation of VOCs in various foods (e.g. for quality control or food degradation studies), as well as being used as a tool for non-invasive medical diagnostics (e.g. human breath analysis). In addition to these fields of study, PTR-MS has been widely used in environmental research, from trace gas analysis in the troposphere to VOC emissions from plants. Participation in two field campaigns (BEWA and ECHO - both part of the German AFO 2000 program) by the Institute of Ion Physics involved a variety of investigations for monitoring biogenic emissions. These included the technique of disjunct eddy covariance for flux measurements above a forest canopy, C-13 carbon labelling experiments to follow carbon use in a plant, and stress-induced VOC emission investigations to gain understanding of how plants react to stress (e.g. ozone exposure). A selection of results from these investigations will be discussed in this presentation. (author)

  6. Eddy covariance emission and deposition flux measurements using proton transfer reaction – time of flight – mass spectrometry (PTR-TOF-MS): comparison with PTR-MS measured vertical gradients and fluxes

    NARCIS (Netherlands)

    Park, J.H.; Goldstein, A.H.; Timkovsky, J|info:eu-repo/dai/nl/330541676; Fares, S.; Weber, R.; Karlik, J.; Holzinger, R.|info:eu-repo/dai/nl/337989338

    2013-01-01

    During summer 2010, a proton transfer reaction – time of flight – mass spectrometer (PTR-TOF-MS) and a quadrupole proton transfer reaction mass spectrometer (PTR-MS) were deployed simultaneously for one month in an orange orchard in the Central Valley of California to collect continuous data

  7. Effects of airflow on odorants' emissions in a model pig house — A laboratory study using Proton-Transfer-Reaction Mass Spectrometry (PTR-MS)

    International Nuclear Information System (INIS)

    Saha, Chayan Kumer; Feilberg, Anders; Zhang, Guoqiang; Adamsen, Anders Peter S.

    2011-01-01

    Identification of different factors that affect emissions of gasses, including volatile organic compounds (VOCs) is necessary to develop emission abatement technology. The objectives of this research were to quantify and study temporal variation of gas emissions from a model pig house under varying ventilation rates. The used model was a 1:12.5 scale of a section of a commercial finishing pig house. The VOC concentrations at inlet, outlet, and slurry pit of the model space were measured using Proton-Transfer-Reaction Mass Spectrometry (PTR-MS). PTR-MS can measure the temporal variations of odor compounds' emission from the slurry pit in real time. The emissions of H 2 S and 14 VOCs were lower compared to real pig buildings except for ammonia, which indicated possible other sources of those compounds than the slurry in the slurry pit. The ventilation rate affected significantly on ammonia and trimethylamine emission (p 2 S) emission was independent of the ventilation rate. VFAs' emission dependency on ventilation rate increased with the increase of carbon chain. Phenols, indoles and ketones showed the positive correlation with ventilation rate to some extent. Generally, compounds with high solubility (low Henry's constant) showed stronger correlation with ventilation rates than the compounds with high Henry's constant.

  8. Comparison of high sensitivity analytical methods (PTR-MS, MIMS, GC-O, SA) and application to food chemistry

    International Nuclear Information System (INIS)

    Boscaini, E.

    2002-10-01

    contributing to the odor profile not detected by FID were detected by PTR-MS. Principal component analysis (PCA) on both GC-0 and PTR-MS data well separated the three cheese samples and showed specific compounds related to each sample. The combination of membrane introduction mass spectrometry (MIMS) and proton transfer reaction mass spectrometry (PTR-MS) is explored in the last session of this thesis. The PTR-MS is used to measure properties of a well-characterized membrane material, poly-dimethylsiloxane (PDMS). It is found that the ability of the PTR-MS to measure absolute concentrations in real-time makes it an ideal tool for the characterization of membrane properties and the interaction of the membrane with multiple organic species. Values for the diffusion coefficients of several molecules are measured and found to be in agreement with literature values. Time modulation of the analyte across the membrane is explored as a method of resolving isobaric interferences for different chemical species. This is demonstrated for acetone and propanal. Finally, the benefit of combining MIMS with PTR-MS is demonstrated by the direct analysis of organic species in the headspace of a hot water solution where the high humidity would not allow analysis using the PTR-MS alone. The effect of membrane thickness and temperature on rise (or response) time and on solubility (or on partition coefficient) can be easily quantified with the use of PTR-MS. Increasing the membrane thickness the rise time increases, the values obtained for the rise time ratios are reasonably close to theoretical values. Temperature increase shows large effects on rise time and solubility. Compounds having stronger interactions with the polymer, i.e. methanol and acetone, are more effected by temperature changing than non-polar compounds, i.e. benzene and toluene. The presence of methyl groups also seems to influence physical properties as response time and solubility. The overall effect of temperature increase is to

  9. Non-methane organic gas emissions from biomass burning: identification, quantification, and emission factors from PTR-ToF during the FIREX 2016 laboratory experiment

    Science.gov (United States)

    Koss, Abigail R.; Sekimoto, Kanako; Gilman, Jessica B.; Selimovic, Vanessa; Coggon, Matthew M.; Zarzana, Kyle J.; Yuan, Bin; Lerner, Brian M.; Brown, Steven S.; Jimenez, Jose L.; Krechmer, Jordan; Roberts, James M.; Warneke, Carsten; Yokelson, Robert J.; de Gouw, Joost

    2018-03-01

    Volatile and intermediate-volatility non-methane organic gases (NMOGs) released from biomass burning were measured during laboratory-simulated wildfires by proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF). We identified NMOG contributors to more than 150 PTR ion masses using gas chromatography (GC) pre-separation with electron ionization, H3O+ chemical ionization, and NO+ chemical ionization, an extensive literature review, and time series correlation, providing higher certainty for ion identifications than has been previously available. Our interpretation of the PTR-ToF mass spectrum accounts for nearly 90 % of NMOG mass detected by PTR-ToF across all fuel types. The relative contributions of different NMOGs to individual exact ion masses are mostly similar across many fires and fuel types. The PTR-ToF measurements are compared to corresponding measurements from open-path Fourier transform infrared spectroscopy (OP-FTIR), broadband cavity-enhanced spectroscopy (ACES), and iodide ion chemical ionization mass spectrometry (I- CIMS) where possible. The majority of comparisons have slopes near 1 and values of the linear correlation coefficient, R2, of > 0.8, including compounds that are not frequently reported by PTR-MS such as ammonia, hydrogen cyanide (HCN), nitrous acid (HONO), and propene. The exceptions include methylglyoxal and compounds that are known to be difficult to measure with one or more of the deployed instruments. The fire-integrated emission ratios to CO and emission factors of NMOGs from 18 fuel types are provided. Finally, we provide an overview of the chemical characteristics of detected species. Non-aromatic oxygenated compounds are the most abundant. Furans and aromatics, while less abundant, comprise a large portion of the OH reactivity. The OH reactivity, its major contributors, and the volatility distribution of emissions can change considerably over the course of a fire.

  10. Non-methane organic gas emissions from biomass burning: identification, quantification, and emission factors from PTR-ToF during the FIREX 2016 laboratory experiment

    Directory of Open Access Journals (Sweden)

    A. R. Koss

    2018-03-01

    Full Text Available Volatile and intermediate-volatility non-methane organic gases (NMOGs released from biomass burning were measured during laboratory-simulated wildfires by proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF. We identified NMOG contributors to more than 150 PTR ion masses using gas chromatography (GC pre-separation with electron ionization, H3O+ chemical ionization, and NO+ chemical ionization, an extensive literature review, and time series correlation, providing higher certainty for ion identifications than has been previously available. Our interpretation of the PTR-ToF mass spectrum accounts for nearly 90 % of NMOG mass detected by PTR-ToF across all fuel types. The relative contributions of different NMOGs to individual exact ion masses are mostly similar across many fires and fuel types. The PTR-ToF measurements are compared to corresponding measurements from open-path Fourier transform infrared spectroscopy (OP-FTIR, broadband cavity-enhanced spectroscopy (ACES, and iodide ion chemical ionization mass spectrometry (I− CIMS where possible. The majority of comparisons have slopes near 1 and values of the linear correlation coefficient, R2, of  >  0.8, including compounds that are not frequently reported by PTR-MS such as ammonia, hydrogen cyanide (HCN, nitrous acid (HONO, and propene. The exceptions include methylglyoxal and compounds that are known to be difficult to measure with one or more of the deployed instruments. The fire-integrated emission ratios to CO and emission factors of NMOGs from 18 fuel types are provided. Finally, we provide an overview of the chemical characteristics of detected species. Non-aromatic oxygenated compounds are the most abundant. Furans and aromatics, while less abundant, comprise a large portion of the OH reactivity. The OH reactivity, its major contributors, and the volatility distribution of emissions can change considerably over the course of a fire.

  11. Formaldehyde measurements by Proton transfer reaction – Mass Spectrometry (PTR-MS: correction for humidity effects

    Directory of Open Access Journals (Sweden)

    A. Vlasenko

    2010-08-01

    Full Text Available Formaldehyde measurements can provide useful information about photochemical activity in ambient air, given that HCHO is formed via numerous oxidation processes. Proton transfer reaction mass spectrometry (PTR-MS is an online technique that allows measurement of VOCs at the sub-ppbv level with good time resolution. PTR-MS quantification of HCHO is hampered by the humidity dependence of the instrument sensitivity, with higher humidity leading to loss of PTR-MS signal. In this study we present an analytical, first principles approach to correct the PTR-MS HCHO signal according to the concentration of water vapor in sampled air. The results of the correction are validated by comparison of the PTR-MS results to those from a Hantzsch fluorescence monitor which does not have the same humidity dependence. Results are presented for an intercomparison made during a field campaign in rural Ontario at Environment Canada's Centre for Atmospheric Research Experiments.

  12. Tropospheric VOC measurements by PTR-MS

    International Nuclear Information System (INIS)

    Hansel, A.; Wisthaler, A.; Graus, M.; Grabmer, W.

    2002-01-01

    Full text: O 3 is formed photochemically from the photolysis of NO 2 , and because O 3 reacts rapidly with NO these reactions result in a photoequilibrium between NO, NO 2 with no net formation or loss of O 3 , However, in the presence of volatile organic compounds (VOCs), the degradation reactions of VOCs lead to the formation of intermediate peroxy radicals which react with NO, converting NO to NO 2 , which then photolyze to form O 3 . Thus, in order to understand quantitatively tropospheric ozone chemistry, it is necessary to know the VOC distribution within the troposphere as well as VOC fluxes from individual sources. Examples will be presented how the use of Proton Transfer Reaction Mass Spectrometry (PTR-MS) has enhanced our understanding of anthropogenic VOC emissions, biosphere-atmosphere exchange processes, and photochemical processing of both anthropogenic and biogenic VOCs in the troposphere. (author)

  13. Comparison of aromatic hydrocarbon measurements made by PTR-MS, DOAS and GC-FID during the MCMA 2003 Field Experiment

    Directory of Open Access Journals (Sweden)

    B. T. Jobson

    2010-02-01

    Full Text Available A comparison of aromatic hydrocarbon measurements is reported for the CENICA supersite in the district of Iztapalapa during the Mexico City Metropolitan Area field experiment in April 2003 (MCMA 2003. Data from three different measurement methods were compared: a Proton Transfer Reaction Mass Spectrometer (PTR-MS, long path measurements using a UV Differential Optical Absorption Spectrometer (DOAS, and Gas Chromatography-Flame Ionization analysis (GC-FID of canister samples. The principle focus was on the comparison between PTR-MS and DOAS data. Lab tests established that the PTR-MS and DOAS calibrations were consistent for a suite of aromatic compounds including benzene, toluene, p-xylene, ethylbenzene, 1,2,4-trimethylbenzene, phenol and styrene. The point sampling measurements by the PTR-MS and GC-FID showed good correlations (r=0.6, and were in reasonable agreement for toluene, C2-alkylbenzenes and C3-alkylbenzenes. The PTR-MS benzene data were consistently high, indicating interference from ethylbenzene fragmentation for the 145 Td drift field intensity used in the experiment. Correlations between the open-path data measured at 16-m height over a 860-m path length (retroreflector in 430 m distance, and the point measurements collected at 37-m sampling height were best for benzene (r=0.61, and reasonably good for toluene, C2-alkylbenzenes, naphthalene, styrene, cresols and phenol (r>0.5. There was good agreement between DOAS and PTR-MS measurements of benzene after correction for the PTR-MS ethylbenzene interference. Mixing ratios measured by DOAS were on average a factor of 1.7 times greater than the PTR-MS data for toluene, C2-alkylbenzenes, naphthalene and styrene. The level of agreement for the toluene data displayed a modest dependence on wind direction, establishing that spatial gradients – horizontal, vertical, or both – in toluene mixing ratios were significant, and

  14. Comparison of Aromatic Hydrocarbon Measurements made by PTR-MS, DOAS and GC-FID during the MCMA 2003 Field Experiment

    International Nuclear Information System (INIS)

    Jobson, Bertram T.; Volkamer, Rainer M.; Velasco, E.; Allwine, Gene; Westberg, Halvor H.; Lamb, Brian K.; Alexander, M.L.; Berkowitz, Carl M.; Molina, Luisa T.

    2010-01-01

    A comparison of aromatic hydrocarbon measurements is reported for the CENICA upersite in the district of Iztapalapa during the Mexico City Metropolitan Area field experiment in April 2003 (MCMA 2003). Data from three different measurement methods were compared: a Proton Transfer Reaction Mass Spectrometer (PTR-MS), long path measurements using a UV Differential Optical Absorption Spectrometer (DOAS), and Gas Chromatography-Flame Ionization analysis (GC-FID) of canister samples. The principle focus was on the comparison between PTR-MS and DOAS data. Lab tests established that the PTR-MS and DOAS calibrations were consistent for a suite of aromatic compounds including benzene, toluene, p-xylene, ethylbenzene, 1,2,4-trimethylbenzene, phenol and styrene. The point sampling measurements by the PTR-MS and GC-FID showed good correlations (r=0.6), and were in reasonable agreement for toluene, C 2 -alkylbenzenes and C3-alkylbenzenes. The PTR-MS benzene data were consistently high, indicating interference from ethylbenzene fragmentation for the 145 Td drift field intensity used in the experiment. Correlations between the open-path data measured at 16-m height over a 860-m path length (retroreflector in 430m distance), and the point measurements collected at 37-m sampling height were best for benzene (r=0.61), and reasonably good for toluene, C2-alkylbenzenes, naphthalene, styrene, cresols and phenol (r>0.5). There was good agreement between DOAS and PTR-MS measurements of benzene after correction for the PTR-MS ethylbenzene interference. Mixing ratios easured by DOAS were on average a factor of 1.7 times greater than the PTR-MS data for toluene, C2-alkylbenzenes, naphthalene and styrene. The level of agreement for the toluene data displayed a modest dependence on wind direction, establishing that spatial gradients - horizontal, vertical, or both - in toluene mixing ratios were significant, and up to a factor of 2 despite the fact that all measurements were conducted above

  15. Ambient measurements of aromatic and oxidized VOCs by PTR-MS and GC-MS: intercomparison between four instruments in a boreal forest in Finland

    Science.gov (United States)

    Kajos, M. K.; Rantala, P.; Hill, M.; Hellén, H.; Aalto, J.; Patokoski, J.; Taipale, R.; Hoerger, C. C.; Reimann, S.; Ruuskanen, T. M.; Rinne, J.; Petäjä, T.

    2015-10-01

    Proton transfer reaction mass spectrometry (PTR-MS) and gas chromatography mass spectrometry GC-MS) are commonly used methods for automated in situ measurements of various volatile organic compounds (VOCs) in the atmosphere. In order to investigate the reliability of such measurements, we operated four automated analyzers using their normal field measurement protocol side by side at a boreal forest site. We measured methanol, acetaldehyde, acetone, benzene and toluene by two PTR-MS and two GC-MS instruments. The measurements were conducted in southern Finland between 13 April and 14 May 2012. This paper presents correlations and biases between the concentrations measured using the four instruments. A very good correlation was found for benzene and acetone measurements between all instruments (the mean R value was 0.88 for both compounds), while for acetaldehyde and toluene the correlation was weaker (with a mean R value of 0.50 and 0.62, respectively). For some compounds, notably for methanol, there were considerable systematic differences in the mixing ratios measured by the different instruments, despite the very good correlation between the instruments (mean R = 0.90). The systematic difference manifests as a difference in the linear regression slope between measurements conducted between instruments, rather than as an offset. This mismatch indicates that the systematic uncertainty in the sensitivity of a given instrument can lead to an uncertainty of 50-100 % in the methanol emissions measured by commonly used methods.

  16. Direct, rapid quantitative analyses of BVOCs using SIFT-MS and PTR-MS obviating sample collection

    Czech Academy of Sciences Publication Activity Database

    Smith, D.; Španěl, Patrik

    2011-01-01

    Roč. 30, č. 7 (2011), s. 945-959 ISSN 0165-9936 Institutional research plan: CEZ:AV0Z40400503 Keywords : SIFT-MS * PTR-MS * Absolute quantification Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 6.273, year: 2011

  17. VOC identification and inter-comparison from laboratory biomass burning using PTR-MS and PIT-MS

    Science.gov (United States)

    C. Warneke; J. M. Roberts; P. Veres; J. Gilman; W. C. Kuster; I. Burling; R. Yokelson; J. A. de Gouw

    2011-01-01

    Volatile organic compounds (VOCs) emitted from fires of biomass commonly found in the southeast and southwest U.S. were investigated with PTR-MS and PIT-MS, which are capable of fast measurements of a large number of VOCs. Both instruments were calibrated with gas standards and mass dependent calibration curves are determined. The sensitivity of the PIT-MS linearly...

  18. Geographical origin classification of olive oils by PTR-MS

    NARCIS (Netherlands)

    Araghipour, N.; Colineau, J.; Koot, A.H.; Akkermans, W.; Rojas, J.M.M.; Beauchamp, J.; Wisthaler, A.; Märk, T.D.; Downey, G.; Guillou, C.; Mannina, L.; Ruth, van S.M.

    2008-01-01

    The volatile compositions of 192 olive oil samples from five different European countries were investigated by PTR-MS sample headspace analysis. The mass spectra of all samples showed many masses with high abundances, indicating the complex VOC composition of olive oil. Three different PLS-DA models

  19. Quality control of meat using proton-transfer-reaction-mass-spectrometry (PTR-MS)

    International Nuclear Information System (INIS)

    Mayr, D.; Hartungen, E.; Maerk, T.D.; Margesin, R.; Schinner, F.

    2002-01-01

    Full text: Numerous food scandals which happened during the last few years make food safety controls more and more important. The method currently used for determining the status of meat, with respect to spoilage, is analysis of the counts of total viable bacteria and/or specific spoilage bacteria. An obvious drawback of this bacteriological method is the long incubation period of 1-3 days that is required for colony formation. Therefore we develop a novel method for meat quality control using PTR-MS which does not have this drawback. We measured the emitted volatile organic compounds (VOCs) of meat (beef and pork) using PTR-MS as a function of storage time. At the same time a bacteriological examination of these meat samples was carried out. We found strong correlations (about 99 %) between some VOCs and bacteriological contamination. This is a first step to replace the time-consuming bacteriological method by fast headspace air measurements to facilitate the investigation of a huge number of pieces of meat in very short time and to determine the maximum storage time and storage temperature from the emissions. We will also use this method to investigate the growth of various bacteria, the changes in the microbial composition and the influence of various environmental conditions such as temperature, pH, chemical and microbial preservation techniques. (author)

  20. PTR-MS analysis of reference and plant-emitted volatile organic compounds

    Science.gov (United States)

    Maleknia, Simin D.; Bell, Tina L.; Adams, Mark A.

    2007-05-01

    Proton transfer reaction-mass spectrometry (PTR-MS) was applied to the analysis of a series of volatile organic compounds (VOCs) that emit from various plants. These include a group of alcohols (methanol, ethanol and butanol), carbonyl-containing compounds (acetic acid, acetone and benzaldehyde), isoprene, acetonitrile, tetrahydrofuran (THF), pyrazine, toluene and xylene and a series of terpenes (p-cymene, camphene, 2-carene, limonene, [beta]-myrcene, [alpha]-pinene, [beta]-pinene, [gamma]-tepinene and terpinolene) and oxygen-containing terpenes (1,8-cineole and linalool). These mass spectral data were compared to an electron ionization (EI) database identifying that not all PTR-MS fragments were common to EI. PTR-MS studies of these reference compounds were utilized to identify VOCs emitted from Eucalyptus grandis leaf at a temperature range of 30-100 °C. In addition to protonated molecules (M + H)+, abundant proton-bound dimers or trimers were detected for alcohols, acetone, acetonitrile and THF. Abundant fragment ions attributed to the loss of water from these proton-bound clusters were also observed. The stability of butyl (C4H9+ m/z 57) and acetyl (CH3CO+ m/z 43) fragment ions directed the proton-transfer reactions of butanol and acetic acid. Abundant (M + H)+ ions were detected for pyrazine, THF, toluene and xylene, as well as for all terpenes except those containing oxygen. For linalool and 1,8-cineole, the loss of water generated an abundant fragment ion at m/z 137. PTR-MS fragmentation patterns for terpenes were proposed for m/z 81 (C6H9+), 93 (C7H9+), 95 (C7H11+), 107 (C8H11+), 109 (C8H13+), 119 (C9H11+), 121 (C9H13+) and 137 (loss of water for oxygen-containing terpenes; C10H17+). The relative abundances of (M + H)+ and fragments for all terpenes (except linalool) were dependent on the drift tube voltage and the optimum voltage for detection of molecular ions was different for various terpenes.

  1. Measuring OVOCs and VOCs by PTR-MS in an urban roadside microenvironment of Hong Kong: relative humidity and temperature dependence, and field intercomparisons

    Science.gov (United States)

    Cui, Long; Zhang, Zhou; Huang, Yu; Lee, Shun Cheng; Blake, Donald Ray; Ho, Kin Fai; Wang, Bei; Gao, Yuan; Wang, Xin Ming; Kwok Keung Louie, Peter

    2016-12-01

    Volatile organic compound (VOC) control is an important issue of air quality management in Hong Kong because ozone formation is generally VOC limited. Several oxygenated volatile organic compound (OVOC) and VOC measurement techniques - namely, (1) offline 2,4-dinitrophenylhydrazine (DNPH) cartridge sampling followed by high-performance liquid chromatography (HPLC) analysis; (2) online gas chromatography (GC) with flame ionization detection (FID); and (3) offline canister sampling followed by GC with mass spectrometer detection (MSD), FID, and electron capture detection (ECD) - were applied during this study. For the first time, the proton transfer reaction-mass spectrometry (PTR-MS) technique was also introduced to measured OVOCs and VOCs in an urban roadside area of Hong Kong. The integrated effect of ambient relative humidity (RH) and temperature (T) on formaldehyde measurements by PTR-MS was explored in this study. A Poly 2-D regression was found to be the best nonlinear surface simulation (r = 0.97) of the experimental reaction rate coefficient ratio, ambient RH, and T for formaldehyde measurement. This correction method was found to be better than correcting formaldehyde concentrations directly via the absolute humidity of inlet sample, based on a 2-year field sampling campaign at Mong Kok (MK) in Hong Kong. For OVOC species, formaldehyde, acetaldehyde, acetone, and MEK showed good agreements between PTR-MS and DNPH-HPLC with slopes of 1.00, 1.10, 0.76, and 0.88, respectively, and correlation coefficients of 0.79, 0.75, 0.60, and 0.93, respectively. Overall, fair agreements were found between PTR-MS and online GC-FID for benzene (slope = 1.23, r = 0.95), toluene (slope = 1.01, r = 0.96) and C2-benzenes (slope = 1.02, r = 0.96) after correcting benzene and C2-benzenes levels which could be affected by fragments formed from ethylbenzene. For the intercomparisons between PTR-MS and offline canister measurements by GC-MSD/FID/ECD, benzene showed good agreement

  2. Airborne measurements of reactive organic trace gases in the atmosphere - with a focus on PTR-MS measurements onboard NASA's flying laboratories

    Science.gov (United States)

    Wisthaler, Armin; Mikoviny, Tomas; Müller, Markus; Schiller, Sven Arne; Feil, Stefan; Hanel, Gernot; Jordan, Alfons; Mutschlechner, Paul; Crawford, James H.; Singh, Hanwant B.; Millet, Dylan

    2017-04-01

    Reactive organic gases (ROGs) play an important role in atmospheric chemistry as they affect the rates of ozone production, particle formation and growth, and oxidant consumption. Measurements of ROGs are analytically challenging because of their large variety and low concentrations in the Earth's atmosphere, and because they are easily affected by measurement artefacts. On aircraft, ROGs are typically measured by canister sampling followed by off-line analysis in the laboratory, fast online gas chromatography or online chemical ionization mass spectrometry. In this work, we will briefly sum up the state-of-the-art in this field before focusing on proton-transfer-reaction mass spectrometry (PTR-MS) and its deployment onboard NASA's airborne science laboratories. We will show how airborne PTR-MS was successfully used in NASA missions for characterizing emissions of ROGs from point sources, for following the photochemical evolution of ROGs in a biomass burning plume, for determining biosphere-atmosphere fluxes of selected ROGs and for validating satellite data. We will also present the airborne PTR-MS instrument in its most recent evolution which includes a radiofrequency ion funnel and ion guide combined with a compact time-of-flight mass spectrometer and discuss its superior performance characteristics. The development of the airborne PTR-MS instrument was supported by the Austrian Federal Ministry for Transport, Innovation and Technology (bmvit) through the Austrian Space Applications Programme (ASAP) of the Austrian Research Promotion Agency (FFG) (grants #833451, #847967). This work was also partly supported by NASA under grant #NNX14AP89G.

  3. Applications of PTR-MS in food flavour research: recent progress and prospects

    International Nuclear Information System (INIS)

    Yeretzian, C.; Pollien, P.; Jordan, A.; Graus, M.; Lindinger, W.

    2002-01-01

    Food products all along the food chain from raw material to final products continuously emit volatile organic compounds (VOs), which are related to important properties of the product itself such as flavor, age, or safety among others. Several analytical techniques for sampling and analysing the head space (HS) of food has been developed, however the proton-transfer-reaction mass spectrometry (PTR-MS) has the particularity to be able to work on real time-basis. By applying PTR-MS two qualitatively distinct types of information were obtained: HS profiles can be averaged over a given time window to yield concentration vs. mass spectra (static data). Such spectra can be used to asses authenticity, monitor deviation in production from a reference or classify product. Alternatively, temporal changes can be analysed via time-intensity plots (dynamic data). As example soluble coffee data is given. (nevyjel)

  4. Does the novel fast-GC coupled with PTR-TOF-MS allow a significant advancement in detecting VOC emissions from plants?

    Czech Academy of Sciences Publication Activity Database

    Pallozzi, E.; Guidolotti, G.; Ciccioli, P.; Brilli, F.; Feil, S.; Calfapietra, Carlo

    2016-01-01

    Roč. 216, JAN (2016), s. 232-240 ISSN 0168-1923 R&D Projects: GA MŠk(CZ) LD13031; GA MŠk(CZ) LO1415 Institutional support: RVO:67179843 Keywords : VOC * Gas chromatography * Time of flight * PTR-TOF-MS * Quercus * eucalyptus Subject RIV: EH - Ecology, Behaviour Impact factor: 3.887, year: 2016

  5. Comparison of three aerosol chemical characterization techniques utilizing PTR-ToF-MS: a study on freshly formed and aged biogenic SOA

    Science.gov (United States)

    Gkatzelis, Georgios I.; Tillmann, Ralf; Hohaus, Thorsten; Müller, Markus; Eichler, Philipp; Xu, Kang-Ming; Schlag, Patrick; Schmitt, Sebastian H.; Wegener, Robert; Kaminski, Martin; Holzinger, Rupert; Wisthaler, Armin; Kiendler-Scharr, Astrid

    2018-03-01

    An intercomparison of different aerosol chemical characterization techniques has been performed as part of a chamber study of biogenic secondary organic aerosol (BSOA) formation and aging at the atmosphere simulation chamber SAPHIR (Simulation of Atmospheric PHotochemistry In a large Reaction chamber). Three different aerosol sampling techniques - the aerosol collection module (ACM), the chemical analysis of aerosol online (CHARON) and the collection thermal-desorption unit (TD) were connected to proton transfer reaction time-of-flight mass spectrometers (PTR-ToF-MSs) to provide chemical characterization of the SOA. The techniques were compared among each other and to results from an aerosol mass spectrometer (AMS) and a scanning mobility particle sizer (SMPS). The experiments investigated SOA formation from the ozonolysis of β-pinene, limonene, a β-pinene-limonene mix and real plant emissions from Pinus sylvestris L. (Scots pine). The SOA was subsequently aged by photo-oxidation, except for limonene SOA, which was aged by NO3 oxidation. Despite significant differences in the aerosol collection and desorption methods of the PTR-based techniques, the determined chemical composition, i.e. the same major contributing signals, was found by all instruments for the different chemical systems studied. These signals could be attributed to known products expected from the oxidation of the examined monoterpenes. The sampling and desorption method of ACM and TD provided additional information on the volatility of individual compounds and showed relatively good agreement. Averaged over all experiments, the total aerosol mass recovery compared to an SMPS varied within 80 ± 10, 51 ± 5 and 27 ± 3 % for CHARON, ACM and TD, respectively. Comparison to the oxygen-to-carbon ratios (O : C) obtained by AMS showed that all PTR-based techniques observed lower O : C ratios, indicating a loss of molecular oxygen either during aerosol sampling or detection. The differences in total

  6. Canopy-scale flux measurements and bottom-up emission estimates of volatile organic compounds from a mixed oak and hornbeam forest in northern Italy

    Science.gov (United States)

    Acton, W. Joe F.; Schallhart, Simon; Langford, Ben; Valach, Amy; Rantala, Pekka; Fares, Silvano; Carriero, Giulia; Tillmann, Ralf; Tomlinson, Sam J.; Dragosits, Ulrike; Gianelle, Damiano; Hewitt, C. Nicholas; Nemitz, Eiko

    2016-06-01

    This paper reports the fluxes and mixing ratios of biogenically emitted volatile organic compounds (BVOCs) 4 m above a mixed oak and hornbeam forest in northern Italy. Fluxes of methanol, acetaldehyde, isoprene, methyl vinyl ketone + methacrolein, methyl ethyl ketone and monoterpenes were obtained using both a proton-transfer-reaction mass spectrometer (PTR-MS) and a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS) together with the methods of virtual disjunct eddy covariance (using PTR-MS) and eddy covariance (using PTR-ToF-MS). Isoprene was the dominant emitted compound with a mean daytime flux of 1.9 mg m-2 h-1. Mixing ratios, recorded 4 m above the canopy, were dominated by methanol with a mean value of 6.2 ppbv over the 28-day measurement period. Comparison of isoprene fluxes calculated using the PTR-MS and PTR-ToF-MS showed very good agreement while comparison of the monoterpene fluxes suggested a slight over estimation of the flux by the PTR-MS. A basal isoprene emission rate for the forest of 1.7 mg m-2 h-1 was calculated using the Model of Emissions of Gases and Aerosols from Nature (MEGAN) isoprene emission algorithms (Guenther et al., 2006). A detailed tree-species distribution map for the site enabled the leaf-level emission of isoprene and monoterpenes recorded using gas-chromatography mass spectrometry (GC-MS) to be scaled up to produce a bottom-up canopy-scale flux. This was compared with the top-down canopy-scale flux obtained by measurements. For monoterpenes, the two estimates were closely correlated and this correlation improved when the plant-species composition in the individual flux footprint was taken into account. However, the bottom-up approach significantly underestimated the isoprene flux, compared with the top-down measurements, suggesting that the leaf-level measurements were not representative of actual emission rates.

  7. Overview of VOC emissions and chemistry from PTR-TOF-MS measurements during the SusKat-ABC campaign: high acetaldehyde, isoprene and isocyanic acid in wintertime air of the Kathmandu Valley

    Science.gov (United States)

    Sarkar, Chinmoy; Sinha, Vinayak; Kumar, Vinod; Rupakheti, Maheswar; Panday, Arnico; Mahata, Khadak S.; Rupakheti, Dipesh; Kathayat, Bhogendra; Lawrence, Mark G.

    2016-03-01

    The Kathmandu Valley in Nepal suffers from severe wintertime air pollution. Volatile organic compounds (VOCs) are key constituents of air pollution, though their specific role in the valley is poorly understood due to insufficient data. During the SusKat-ABC (Sustainable Atmosphere for the Kathmandu Valley-Atmospheric Brown Clouds) field campaign conducted in Nepal in the winter of 2012-2013, a comprehensive study was carried out to characterise the chemical composition of ambient Kathmandu air, including the determination of speciated VOCs, by deploying a proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS) - the first such deployment in South Asia. In the study, 71 ion peaks (for which measured ambient concentrations exceeded the 2σ detection limit) were detected in the PTR-TOF-MS mass scan data, highlighting the chemical complexity of ambient air in the valley. Of the 71 species, 37 were found to have campaign average concentrations greater than 200 ppt and were identified based on their spectral characteristics, ambient diel profiles and correlation with specific emission tracers as a result of the high mass resolution (m / Δm > 4200) and temporal resolution (1 min) of the PTR-TOF-MS. The concentration ranking in the average VOC mixing ratios during our wintertime deployment was acetaldehyde (8.8 ppb) > methanol (7.4 ppb) > acetone + propanal (4.2 ppb) > benzene (2.7 ppb) > toluene (1.5 ppb) > isoprene (1.1 ppb) > acetonitrile (1.1 ppb) > C8-aromatics ( ˜ 1 ppb) > furan ( ˜ 0.5 ppb) > C9-aromatics (0.4 ppb). Distinct diel profiles were observed for the nominal isobaric compounds isoprene (m / z = 69.070) and furan (m / z = 69.033). Comparison with wintertime measurements from several locations elsewhere in the world showed mixing ratios of acetaldehyde ( ˜ 9 ppb), acetonitrile ( ˜ 1 ppb) and isoprene ( ˜ 1 ppb) to be among the highest reported to date. Two "new" ambient compounds, namely formamide (m / z = 46.029) and acetamide (m / z

  8. Development and deployment of a compact PTR-ToF-MS for Suborbital Research on the Earth's Atmospheric Composition

    Science.gov (United States)

    Müller, Markus; Mikoviny, Tomas; Haidacher, Stefan; Hanel, Gernot; Hartungen, Eugen; Jordan, Alfons; Märk, Lukas; Mutschlechner, Paul; Schottkowsky, Ralf; Sulzer, Philipp; Crawford, James H.; Wisthaler, Armin

    2014-05-01

    We report the development of a compact Proton-Transfer-Reaction Time-of-Flight Mass Spectrometer (PTR-ToF-MS) in support of NASA's suborbital research program on the Earth's atmospheric composition. A lightweight, low mass resolution orthogonal acceleration ToF-MS was developed and combined with a conventional PTR ion source to measure volatile organic compounds (VOCs) in real time. The instrument was specially designed to resist aircraft vibrations and rough conditions during boundary layer flights, take-off and landing. The compact PTR-ToF-MS generates full mass spectral information at 1-second time resolution and below. With sensitivities of up to 150 cps/ppbv, typical 2σ detection limits in the range from 0.06 to 0.48 ppbv for a 1-second signal integration are achieved. A mass resolving power m/Δm of up to 1700 combined with an absolute mass accuracy and reproducibility of less than 3 mDa make it possible to distinguish isobaric ions at high time resolution, e.g. humidity- dependent isobaric background ions. The prototype instrument was successfully deployed for in-situ measurements of VOCs onboard the NASA P-3B Airborne Science Laboratory during two DISCOVER-AQ campaigns in the San Joaquin Valley, CA, and in Houston, TX, 2013. A 1-second time resolution results in a horizontal spatial resolution of typically 110 m and a vertical spatial resolution of typically 8 m which allowed for the quantitative detection of the entire suite of VOCs in strongly localized emission plumes from industrial, agricultural and biomass-burning sources. This work was funded by BMVIT / FFG-ALR in the frame of the Austrian Space Application Programme (ASAP 8, project 833451). Additional resources were provided through NASA's Earth Venture program (EV-1) and the NASA Postdoctoral Program (NPP).

  9. Comparison of three aerosol chemical characterization techniques utilizing PTR-ToF-MS: a study on freshly formed and aged biogenic SOA

    Directory of Open Access Journals (Sweden)

    G. I. Gkatzelis

    2018-03-01

    Full Text Available An intercomparison of different aerosol chemical characterization techniques has been performed as part of a chamber study of biogenic secondary organic aerosol (BSOA formation and aging at the atmosphere simulation chamber SAPHIR (Simulation of Atmospheric PHotochemistry In a large Reaction chamber. Three different aerosol sampling techniques – the aerosol collection module (ACM, the chemical analysis of aerosol online (CHARON and the collection thermal-desorption unit (TD were connected to proton transfer reaction time-of-flight mass spectrometers (PTR-ToF-MSs to provide chemical characterization of the SOA. The techniques were compared among each other and to results from an aerosol mass spectrometer (AMS and a scanning mobility particle sizer (SMPS. The experiments investigated SOA formation from the ozonolysis of β-pinene, limonene, a β-pinene–limonene mix and real plant emissions from Pinus sylvestris L. (Scots pine. The SOA was subsequently aged by photo-oxidation, except for limonene SOA, which was aged by NO3 oxidation. Despite significant differences in the aerosol collection and desorption methods of the PTR-based techniques, the determined chemical composition, i.e. the same major contributing signals, was found by all instruments for the different chemical systems studied. These signals could be attributed to known products expected from the oxidation of the examined monoterpenes. The sampling and desorption method of ACM and TD provided additional information on the volatility of individual compounds and showed relatively good agreement. Averaged over all experiments, the total aerosol mass recovery compared to an SMPS varied within 80 ± 10, 51 ± 5 and 27 ± 3 % for CHARON, ACM and TD, respectively. Comparison to the oxygen-to-carbon ratios (O : C obtained by AMS showed that all PTR-based techniques observed lower O : C ratios, indicating a loss of molecular oxygen either during aerosol sampling or

  10. Canopy-scale flux measurements and bottom-up emission estimates of volatile organic compounds from a mixed oak and hornbeam forest in northern Italy

    Directory of Open Access Journals (Sweden)

    W. J. F. Acton

    2016-06-01

    Full Text Available This paper reports the fluxes and mixing ratios of biogenically emitted volatile organic compounds (BVOCs 4 m above a mixed oak and hornbeam forest in northern Italy. Fluxes of methanol, acetaldehyde, isoprene, methyl vinyl ketone + methacrolein, methyl ethyl ketone and monoterpenes were obtained using both a proton-transfer-reaction mass spectrometer (PTR-MS and a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS together with the methods of virtual disjunct eddy covariance (using PTR-MS and eddy covariance (using PTR-ToF-MS. Isoprene was the dominant emitted compound with a mean daytime flux of 1.9 mg m−2 h−1. Mixing ratios, recorded 4 m above the canopy, were dominated by methanol with a mean value of 6.2 ppbv over the 28-day measurement period. Comparison of isoprene fluxes calculated using the PTR-MS and PTR-ToF-MS showed very good agreement while comparison of the monoterpene fluxes suggested a slight over estimation of the flux by the PTR-MS. A basal isoprene emission rate for the forest of 1.7 mg m−2 h−1 was calculated using the Model of Emissions of Gases and Aerosols from Nature (MEGAN isoprene emission algorithms (Guenther et al., 2006. A detailed tree-species distribution map for the site enabled the leaf-level emission of isoprene and monoterpenes recorded using gas-chromatography mass spectrometry (GC–MS to be scaled up to produce a bottom-up canopy-scale flux. This was compared with the top-down canopy-scale flux obtained by measurements. For monoterpenes, the two estimates were closely correlated and this correlation improved when the plant-species composition in the individual flux footprint was taken into account. However, the bottom-up approach significantly underestimated the isoprene flux, compared with the top-down measurements, suggesting that the leaf-level measurements were not representative of actual emission rates.

  11. Volatile compound changes during shelf life of dried Boletus edulis: comparison between SPME-GC-MS and PTR-ToF-MS analysis.

    Science.gov (United States)

    Aprea, Eugenio; Romano, Andrea; Betta, Emanuela; Biasioli, Franco; Cappellin, Luca; Fanti, Marco; Gasperi, Flavia

    2015-01-01

    Drying process is commonly used to allow long time storage of valuable porcini mushrooms (Boletus edulis). Although considered a stable product dried porcini flavour changes during storage. Monitoring of volatile compounds during shelf life may help to understand the nature of the observed changes. In the present work two mass spectrometric techniques were used to monitor the evolution of volatile compounds during commercial shelf life of dried porcini. Solid phase microextraction (SPME) coupled to gas chromatography - mass spectrometry (GC-MS) allowed the identification of 66 volatile compounds, 36 of which reported for the first time, monitored during the commercial shelf life of dried porcini. Proton transfer reaction - time of flight - mass spectrometry (PTR-ToF-MS) , a direct injection mass spectrometric technique, was shown to be a fast and sensitive instrument for the general monitoring of volatile compound evolution during storage of dried porcini. Furthermore, PTR-ToF-MS grants access to compounds whose determination would otherwise require lengthy pre-concentration and/or derivatization steps such as ammonia and small volatile amines. The two techniques, both used for the first time to study dried porcini, provided detailed description of time evolution of volatile compounds during shelf life. Alcohols, aldehydes, ketones and monoterpenes diminish during the storage while carboxylic acids, pyrazines, lactones and amines increase. The storage temperature modifies the rate of the observed changes influencing the final quality of the dried porcini. We showed the advantages of both techniques, suggesting a strategy to be adopted to follow time evolution of volatile compounds in food products during shelf life, based on the identification of compounds by GC-MS and the rapid time monitoring by PTR-ToF-MS measurements in order to maximize the advantages of both techniques. Copyright © 2015 John Wiley & Sons, Ltd.

  12. Measurements of VOC fluxes by Eddy-covariance with a PTR-Qi-TOF-MS over a mature wheat crop near Paris: Evaluation of data quality and uncertainties.

    Science.gov (United States)

    Buysse, Pauline; Loubet, Benjamin; Ciuraru, Raluca; Lafouge, Florence; Zurfluh, Olivier; Gonzaga-Gomez, Lais; Fanucci, Olivier; Gueudet, Jean-Christophe; Decuq, Céline; Gros, Valérie; Sarda, Roland; Zannoni, Nora

    2017-04-01

    The quantification of volatile organic compounds (VOC) fluxes exchanged by terrestrial ecosystems is of large interest because of their influence on the chemistry and composition of the atmosphere including aerosols and oxidants. Latest developments in the techniques for detecting, identifying and measuring VOC fluxes have considerably improved the abilities to get reliable estimates. Among these, the eddy-covariance (EC) methodology constitutes the most direct approach, and relies on both well-established principles (Aubinet et al. 2000) and a sound continuously worldwide improving experience. The combination of the EC methodology with the latest proton-transfer-reaction mass spectrometer (PTR-MS) device, the PTR-Qi-TOF-MS, which allows the identification and quantification of more than 500 VOC at high frequency, now provides a very powerful and precise tool for an accurate quantification of VOC fluxes on various types of terrestrial ecosystems. The complexity of the whole methodology however demands that several data quality requirements are fulfilled. VOC fluxes were measured by EC with a PTR-Qi-TOF-MS (national instrument within the ANAEE-France framework) for one month and a half over a mature wheat crop near Paris (FR-GRI ICOS site). Most important emissions (by descending order) were observed from detected compounds with mass-over-charge (m/z) ratios of 33.033 (methanol), 45.033 (acetaldehyde), 93.033 (not identified yet), 59.049 (acetone), and 63.026 (dimethyl sulfide or DMS). Emissions from higher-mass compounds, which might be due to pesticide applications at the beginning of our observation period, were also detected. Some compounds were also seen to deposit (e.g. m/z 47.013, 71.085, 75.044, 83.05) while others exhibited bidirectional fluxes (e.g. m/z 57.07, 69.07). Before analyzing VOC flux responses to meteorological and crop development drivers, a data quality check was performed which included (i) uncertainty analysis of mass and concentration

  13. Investigation on the spoiling of meat using PTR-MS

    International Nuclear Information System (INIS)

    Mayr, D.; Maerk, T.D.; Margesin, R.; Schinner, F.

    2002-01-01

    The spoiling of meat was investigated. Beef (pork) were wrapped into different kinds of packages (air and vacuum) and stored at 4 o C for 10 (13) days. The emitted volatile organic compounds (VOCs) in the course of time were measured and a large increase in these emissions after a few days of storage was found. Also a large difference in the spoiling behavior between vacuum- and air- packed meat was observed. The measurements were performed using a proton-transfer-reaction-mass spectrometer(PTR-MS) system, it allows on-line monitoring of volatile organic compounds (VOCs) concentrations. Ethylacetate, methylpropionate, and propylformate were detected as typical spoiling compounds in pork samples. After 3.5 days the concentrations started to exponentially increase, but after 6 days remained more or less unchanged. This VOCs behaviour corresponds to a typical bacterial growth curve. Therefore, it was concluded that bacteria produce these components. In a second measurements set, the VOCs emitted by beef under aerobic (normal packed) and anaerobic (vacuum packed) conditions were compared. In the case of normal air-packed beef, the above mentioned spoiling compounds strongly increased with the time, while with the vacuum-packed beef a strong increase of ethanol was detected. This method as a replacement of the bacteriological examinations of meat spoilage is proposed. (nevyjel)

  14. Discrimination of Polish unifloral honeys using overall PTR-MS and HPLC fingerprints combined with chemometrics

    NARCIS (Netherlands)

    Kus, P.M.; Ruth, van S.M.

    2015-01-01

    A total of 62 honey samples of six floral origins (rapeseed, lime, heather, cornflower, buckwheat and black locust) were analysed by means of proton transfer reaction mass spectrometry (PTR-MS) and HPLC-DAD. The data were evaluated by principal component analysis and k-nearest neighbours

  15. Explosives and chemical warfare agents - detection and analysis with PTR-MS

    Energy Technology Data Exchange (ETDEWEB)

    Sulzer, Philipp; Juerschik, Simone; Jaksch, Stefan; Jordan, Alfons; Hanel, Gernot; Hartungen, Eugen; Seehauser, Hans; Maerk, Lukas; Haidacher, Stefan; Schottkowsky, Ralf [IONICON Analytik GmbH, Innsbruck (Austria); Petersson, Fredrik [Institut fuer Ionenphysik und Angewandte Physik, Leopold-Franzens Universitaet Innsbruck (Austria); Maerk, Tilmann [IONICON Analytik GmbH, Innsbruck (Austria); Institut fuer Ionenphysik und Angewandte Physik, Leopold-Franzens Universitaet Innsbruck (Austria)

    2010-07-01

    We utilized a recently developed high sensitivity PTR-MS instrument equipped with a high resolution time-of-flight mass analyzer for detailed investigations on explosives and chemical warfare agents (CWAs). We show that with this so called PTR-TOF 8000 it is possible to identify solid explosives (RDX, TNT, HMX, PETN and Semtex A) by analyzing the headspace above small quantities of samples at room temperature and from trace quantities not visible to the naked eye placed on surfaces. As the mentioned solid explosives possess very low vapor pressures, the main challenge for detecting them in the gas phase is to provide an instrument with a sufficient sensitivity. CWAs on the other side have very high vapor pressures but are difficult to identify unambiguously as their nominal molecular masses are usually comparably small and therefore hard to distinguish from harmless everyday-compounds (e.g. mustard gas: 159 g/mol). In the present work we demonstrate that we can detect a broad range of dangerous substances, ranging from the CWA mustard gas to the explosive HMX.

  16. Volatile organic compound (VOC) emissions characterization during the flow-back phase of a hydraulically refractured well in the Uintah Basin, Utah using mobile PTR-MS measurements

    Science.gov (United States)

    Geiger, F.; Warneke, C.; Brown, S. S.; De Gouw, J. A.; Dube, W. P.; Edwards, P.; Gilman, J.; Graus, M.; Helleis, F.; Kofler, J.; Lerner, B. M.; Orphal, J.; Petron, G.; Roberts, J. M.; Zahn, A.

    2014-12-01

    Ongoing improvements in advanced technologies for crude oil and natural gas extraction from unconventional reserves, such as directional drilling and hydraulic fracturing, have greatly increased the production of fossil fuels within recent years. The latest forecasts even estimate an enhancement of 56% in total natural gas production due to increased development of shale gas, tight gas and offshore natural gas resources from 2012 to 2040 with the largest contribution from shale formations [US EIA: Annual Energy Outlook 2014]. During the field intensive 'Energy and Environment - Uintah Basin Winter Ozone Study (UBWOS)', measurements of volatile organic compounds (VOCs) were made using proton-transfer-reactions mass spectrometry (PTR-MS) at the ground site Horse Pool and using a mobile laboratory in the Uintah Basin, Utah, which is a region well known for intense fossil fuel production. A reworked gas well in the Red Wash fields was sampled regularly within two weeks performing mobile laboratory measurements downwind of the well site. The well had been recently hydraulically refractured at that time and waste water was collected into an open flow-back pond. Very high mixing ratios of aromatic hydrocarbons (C6-C13) up to the ppm range were observed coming from condensate and flow-back reservoirs. The measurements are used to determine sources of specific VOC emissions originating from the different parts of the well site and mass spectra are used to classify the air composition in contrast to samples taken at the Horse Pool field site and crude oil samples from South Louisiana. Enhancement ratios and time series of measured peak values for aromatics showed no clear trend, which indicates changes in emissions with operations at the site.

  17. Effects of air exchange, temperature and slurry management on odorant emissions from pig production units and slurry tanks studied by proton-transfer-reaction mass spectrometry (PTR-MS)

    Energy Technology Data Exchange (ETDEWEB)

    Feilberg, A.; Adamsen, A.P.S.; Liu, D.; Hansen, M.J.; Bildsoe, P. [Aarhus Univ., Tjele (Denmark). Dept. of Biosystems Engineering

    2010-07-01

    The factors affecting the variability of odorant emissions from intensive pig production facilities were examined using proton-transfer-reaction mass spectrometry (PTR-MS) to monitor emissions of odorants. Quantitative and time-resolved results for protonated ions representing hydrogen sulphide (H{sub 2}S), volatile organic sulphur compounds, organic amines, volatile carboxylic acids, carbonyls, phenols and indoles can be obtained. This study presented the results from PTRMS measurements of odorant emissions from finisher pig houses and finisher manure storage tanks. The measurements were performed at an experimental full-scale pig section with mechanical ventilation and at an experimental manure storage facility with controlled air exchange. Field measurements were taken during variable air exchange rates and temperatures, during finisher growth, and during emptying of the slurry pit. The results revealed a pronounced diurnal variation in emissions of odorants from the pig section with peaks in daytime coinciding with the highest ventilation rates and highest room temperatures. The highest emission rates were observed for H{sub 2}S and carboxylic acids. Based on odour threshold values, methanethiol and 4-methylphenol were estimated to contribute considerably to the odour nuisance. Discharging of the slurry pit led to reduced H{sub 2}S emissions, but peaks of H{sub 2}S were observed during manure handling.

  18. Compounds enhanced in a mass spectrometric profile of smokers' exhaled breath versus non-smokers as determined in a pilot study using PTR-MS.

    Science.gov (United States)

    Kushch, Ievgeniia; Schwarz, Konrad; Schwentner, Lukas; Baumann, Bettina; Dzien, Alexander; Schmid, Alex; Unterkofler, Karl; Gastl, Günter; Spaněl, Patrik; Smith, David; Amann, Anton

    2008-06-01

    A pilot study has been carried out to define typical characteristics of the trace gas compounds in exhaled breath of non-smokers and smokers to assist interpretation of breath analysis data from patients who smoke with respiratory diseases and lung cancer. Exhaled breath was analyzed using proton transfer reaction-mass spectrometry (PTR-MS) for 370 volunteers (81 smokers, 210 non-smokers, 79 ex-smokers). Volatile organic compounds corresponding to product ions at seven mass-to-charge ratios (m/z 28, 42, 69, 79, 93, 97, 123) in the PTR-MS spectra differentiated between smokers and non-smokers. The Youden index (= maximum of sensitivity + specificity - 1, YI) as a measure for differentiation between smokers and non-smokers was YI = 0.43 for ions at the m/z values 28 (tentatively identified as HCN), YI = 0.75 for m/z = 42 (tentatively identified as acetonitrile) and YI = 0.53 for m/z = 79 (tentatively identified as benzene). No statistically significant difference between smokers and non-smokers was observed for the product ions at m/z = 31 and 33 (compounds tentatively identified as formaldehyde and methanol). When interpreting the exhaled breath of lung cancer or COPD patients, who often smoke, compounds appearing at the above-mentioned seven mass-to-charge ratios should be considered with appropriate care to avoid misdiagnosis. Validation studies in larger numbers of patients with more precise delineation of their smoking behavior and using additional analytical techniques such as GC/MS and SIFT-MS should be carried out.

  19. Proton-transfer reaction mass spectrometry (PTR-MS) for the authentication of regionally unique South African lamb

    NARCIS (Netherlands)

    Erasmus, Sara W.; Muller, Magdalena; Alewijn, Martin; Koot, Alex H.; Ruth, van Saskia M.; Hoffman, Louwrens C.

    2017-01-01

    The volatile fingerprints of South African lamb meat and fat were measured by proton-transfer mass spectrometry (PTR-MS) to evaluate it as an authentication tool. Meat and fat of the Longissimus lumborum (LL) of lambs from six different regions were assessed. Analysis showed that the volatile

  20. Overview of VOC emissions and chemistry from PTR-TOF-MS measurements during the SusKat-ABC campaign: high acetaldehyde, isoprene and isocyanic acid in wintertime air of the Kathmandu Valley

    Directory of Open Access Journals (Sweden)

    C. Sarkar

    2016-03-01

    Full Text Available The Kathmandu Valley in Nepal suffers from severe wintertime air pollution. Volatile organic compounds (VOCs are key constituents of air pollution, though their specific role in the valley is poorly understood due to insufficient data. During the SusKat-ABC (Sustainable Atmosphere for the Kathmandu Valley–Atmospheric Brown Clouds field campaign conducted in Nepal in the winter of 2012–2013, a comprehensive study was carried out to characterise the chemical composition of ambient Kathmandu air, including the determination of speciated VOCs, by deploying a proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS – the first such deployment in South Asia. In the study, 71 ion peaks (for which measured ambient concentrations exceeded the 2σ detection limit were detected in the PTR-TOF-MS mass scan data, highlighting the chemical complexity of ambient air in the valley. Of the 71 species, 37 were found to have campaign average concentrations greater than 200 ppt and were identified based on their spectral characteristics, ambient diel profiles and correlation with specific emission tracers as a result of the high mass resolution (m ∕ Δm  >  4200 and temporal resolution (1 min of the PTR-TOF-MS. The concentration ranking in the average VOC mixing ratios during our wintertime deployment was acetaldehyde (8.8 ppb  >  methanol (7.4 ppb  >  acetone + propanal (4.2 ppb  >  benzene (2.7 ppb  >  toluene (1.5 ppb  >  isoprene (1.1 ppb  >  acetonitrile (1.1 ppb  >  C8-aromatics ( ∼ 1 ppb  >  furan ( ∼ 0.5 ppb  >  C9-aromatics (0.4 ppb. Distinct diel profiles were observed for the nominal isobaric compounds isoprene (m ∕ z  =  69.070 and furan (m ∕ z  =  69.033. Comparison with wintertime measurements from several locations elsewhere in the world showed mixing ratios of acetaldehyde ( ∼  9 ppb, acetonitrile ( ∼  1 ppb and isoprene

  1. Ground-based PTR-MS measurements of reactive organic compounds during the MINOS campaign in Crete, July–August 2001

    Directory of Open Access Journals (Sweden)

    G. Salisbury

    2003-01-01

    Full Text Available This study presents measurements of acetonitrile, benzene, toluene, methanol and acetone made using the proton-transfer-reaction mass spectrometry (PTR-MS technique at the Finokalia ground station in Crete during the Mediterranean INtensive Oxidant Study (MINOS in July-August 2001. Three periods during the campaign with broadly consistent back trajectories are examined in detail. In the first, air was advected from Eastern Europe without significant biomass burning influence (mean acetonitrile mixing ratio 154 pmol/mol. In the second period, the sampled air masses originated in Western Europe, and were advected approximately east-south-east, before turning south-west over the Black Sea and north-western Turkey. The third well-defined period included air masses advected from Eastern Europe passing east and south of/over the Sea of Azov, and showed significant influence by biomass burning (mean acetonitrile mixing ratio 436 pmol/mol, confirmed by satellite pictures. The mean toluene:benzene ratios observed in the three campaign periods described were 0.35, 0.37 and 0.22, respectively; the use of this quantity to determine air mass age is discussed. Methanol and acetone were generally well-correlated both with each other and with carbon monoxide throughout the campaign. Comparison of the acetone and methanol measurements with the MATCH-MPIC model showed that the model underestimated both species by a factor of 4, on average. The correlations between acetone, methanol and CO implied that the relatively high levels of methanol observed during MINOS were largely due to direct biogenic emissions, and also that biogenic sources of acetone were highly significant during MINOS (~35%. This in turn suggests that the model deficit in both species may be due, at least in part, to missing biogenic emissions.

  2. Investigation of the aroma of commercial peach (Prunus persica L. Batsch) types by Proton Transfer Reaction-Mass Spectrometry (PTR-MS) and sensory analysis.

    Science.gov (United States)

    Bianchi, Tiago; Weesepoel, Yannick; Koot, Alex; Iglesias, Ignasi; Eduardo, Iban; Gratacós-Cubarsí, Marta; Guerrero, Luis; Hortós, Maria; van Ruth, Saskia

    2017-09-01

    The aim of this study was to investigate the aroma and sensory profiles of various types of peaches (Prunus persica L. Batsch.). Forty-three commercial cultivars comprising peaches, flat peaches, nectarines, and canning peaches (pavías) were grown over two consecutive harvest years. Fruits were assessed for chemical aroma and sensory profiles. Chemical aroma profile was obtained by proton transfer reaction-mass spectrometry (PTR-MS) and spectral masses were tentatively identified with PTR-Time of Flight-MS (PTR-Tof-MS). Sensory analysis was performed at commercial maturity considering seven aroma/flavor attributes. The four types of peaches showed both distinct chemical aroma and sensory profiles. Flat peaches and canning peaches showed most distinct patterns according to discriminant analysis. The sensory data were related to the volatile compounds by partial least square regression. γ-Hexalactone, γ-octalactone, hotrienol, acetic acid and ethyl acetate correlated positively, and benzeneacetaldehyde, trimethylbenzene and acetaldehyde negatively to the intensities of aroma and ripe fruit sensory scores. Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. Measurements of volatile organic compounds at a suburban ground site (T1 in Mexico City during the MILAGRO 2006 campaign: measurement comparison, emission ratios, and source attribution

    Directory of Open Access Journals (Sweden)

    D. M. Bon

    2011-03-01

    Full Text Available Volatile organic compound (VOC mixing ratios were measured with two different instruments at the T1 ground site in Mexico City during the Megacity Initiative: Local and Global Research Observations (MILAGRO campaign in March of 2006. A gas chromatograph with flame ionization detector (GC-FID quantified 18 light alkanes, alkenes and acetylene while a proton-transfer-reaction ion-trap mass spectrometer (PIT-MS quantified 12 VOC species including oxygenated VOCs (OVOCs and aromatics. A GC separation system was used in conjunction with the PIT-MS (GC-PIT-MS to evaluate PIT-MS measurements and to aid in the identification of unknown VOCs. The VOC measurements are also compared to simultaneous canister samples and to two independent proton-transfer-reaction mass spectrometers (PTR-MS deployed on a mobile and an airborne platform during MILAGRO. VOC diurnal cycles demonstrate the large influence of vehicle traffic and liquid propane gas (LPG emissions during the night and photochemical processing during the afternoon. Emission ratios for VOCs and OVOCs relative to CO are derived from early-morning measurements. Average emission ratios for non-oxygenated species relative to CO are on average a factor of ~2 higher than measured for US cities. Emission ratios for OVOCs are estimated and compared to literature values the northeastern US and to tunnel studies in California. Positive matrix factorization analysis (PMF is used to provide insight into VOC sources and processing. Three PMF factors were distinguished by the analysis including the emissions from vehicles, the use of liquid propane gas and the production of secondary VOCs + long-lived species. Emission ratios to CO calculated from the results of PMF analysis are compared to emission ratios calculated directly from measurements. The total PIT-MS signal is summed to estimate the fraction of identified versus unidentified VOC species.

  4. Measurements of volatile organic compounds at a suburban ground site (T1) in Mexico City during the MILAGRO 2006 campaign: Measurement comparison, emission ratios, and source attribution

    Energy Technology Data Exchange (ETDEWEB)

    Bon, D.M.; Springston, S.; M.Ulbrich, I.; de Gouw, J. A.; Warneke, C.; Kuster, W. C.; Alexander, M. L.; Baker, A.; Beyersdorf, A. J.; Blake, D.; Fall, R.; Jimenez, J. L., Herndon, S. C.; Huey, L. G.; Knighton, W. B.; Ortega, J.; Vargas, O.

    2011-03-16

    Volatile organic compound (VOC) mixing ratios were measured with two different instruments at the T1 ground site in Mexico City during the Megacity Initiative: Local and Global Research Observations (MILAGRO) campaign in March of 2006. A gas chromatograph with flame ionization detector (GC-FID) quantified 18 light alkanes, alkenes and acetylene while a proton-transfer-reaction ion-trap mass spectrometer (PIT-MS) quantified 12 VOC species including oxygenated VOCs (OVOCs) and aromatics. A GC separation system was used in conjunction with the PIT-MS (GC-PIT-MS) to evaluate PIT-MS measurements and to aid in the identification of unknown VOCs. The VOC measurements are also compared to simultaneous canister samples and to two independent proton-transfer-reaction mass spectrometers (PTR-MS) deployed on a mobile and an airborne platform during MILAGRO. VOC diurnal cycles demonstrate the large influence of vehicle traffic and liquid propane gas (LPG) emissions during the night and photochemical processing during the afternoon. Emission ratios for VOCs and OVOCs relative to CO are derived from early-morning measurements. Average emission ratios for non-oxygenated species relative to CO are on average a factor of {approx}2 higher than measured for US cities. Emission ratios for OVOCs are estimated and compared to literature values the northeastern US and to tunnel studies in California. Positive matrix factorization analysis (PMF) is used to provide insight into VOC sources and processing. Three PMF factors were distinguished by the analysis including the emissions from vehicles, the use of liquid propane gas and the production of secondary VOCs + long-lived species. Emission ratios to CO calculated from the results of PMF analysis are compared to emission ratios calculated directly from measurements. The total PIT-MS signal is summed to estimate the fraction of identified versus unidentified VOC species.

  5. Biogenic volatile organic compound analyses by PTR-TOF-MS: Calibration, humidity effect and reduced electric field dependency.

    Science.gov (United States)

    Pang, Xiaobing

    2015-06-01

    Green leaf volatiles (GLVs) emitted by plants after stress or damage induction are a major part of biogenic volatile organic compounds (BVOCs). Proton transfer reaction time-of-flight mass spectrometry (PTR-TOF-MS) is a high-resolution and sensitive technique for in situ GLV analyses, while its performance is dramatically influenced by humidity, electric field, etc. In this study the influence of gas humidity and the effect of reduced field (E/N) were examined in addition to measuring calibration curves for the GLVs. Calibration curves measured for seven of the GLVs in dry air were linear, with sensitivities ranging from 5 to 10 ncps/ppbv (normalized counts per second/parts per billion by volume). The sensitivities for most GLV analyses were found to increase by between 20% and 35% when the humidity of the sample gas was raised from 0% to 70% relative humidity (RH) at 21°C, with the exception of (E)-2-hexenol. Product ion branching ratios were also affected by humidity, with the relative abundance of the protonated molecular ions and higher mass fragment ions increasing with humidity. The effect of reduced field (E/N) on the fragmentation of GLVs was examined in the drift tube of the PTR-TOF-MS. The structurally similar GLVs are acutely susceptible to fragmentation following ionization and the fragmentation patterns are highly dependent on E/N. Overall the measured fragmentation patterns contain sufficient information to permit at least partial separation and identification of the isomeric GLVs by looking at differences in their fragmentation patterns at high and low E/N. Copyright © 2015. Published by Elsevier B.V.

  6. Real-time profiling of organic trace gases in the planetary boundary layer by PTR-MS using a tethered balloon

    Directory of Open Access Journals (Sweden)

    R. Schnitzhofer

    2009-12-01

    Full Text Available A method for real-time profiling of volatile organic compounds (VOCs was developed combining the advantages of a tethered balloon as a research platform and of proton transfer reaction mass spectrometry (PTR-MS as an analytical technique for fast and highly sensitive VOC measurements. A 200 m Teflon tube was used to draw sampling air from a tethered aerodynamic balloon to the PTR-MS instrument. Positive and negative artefacts (i.e. formation and loss of VOCs in the tube were characterised in the laboratory and in the field by a set of 11 atmospherically relevant VOCs including both pure and oxygenated hydrocarbons. The only two compounds that increased or decreased when sampled through the tube were acetone (+7% and xylene (-6%. The method was successfully deployed during a winter field campaign to determine the small scale spatial and temporal patterns of air pollutants under winter inversion conditions.

  7. Airborne Deployment of a High Resolution PTR-ToF-MS to Characterize Non-methane Organic Gases in Wildfire Smoke: A Pilot Study During WE-CAN Test Flights

    Science.gov (United States)

    Permar, W.; Hu, L.; Fischer, E. V.

    2017-12-01

    Despite being the second largest primary source of tropospheric volatile organic compounds (VOCs), biomass burning is poorly understood relative to other sources due in part to its large variability and the difficulty inherent to sampling smoke. In light of this, several field campaigns are planned to better characterize wildfire plume emissions and chemistry through airborne sampling of smoke plumes. As part of this effort, we will deploy a high-resolution proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS) on the NSF/NCAR C-130 research aircraft during the collaborative Western wildfire Experiment for Cloud chemistry, Aerosol absorption and Nitrogen (WE-CAN) mission. PTR-ToF-MS is well suited for airborne measurements of VOC in wildfire smoke plumes due to its ability to collect real time, high-resolution data for the full mass range of ionizable organic species, many of which remain uncharacterized or unidentified. In this work, we will report on our initial measurements from the WE-CAN test flights in September 2017. We will also discuss challenges associated with deploying the instrument for airborne missions targeting wildfire smoke and goals for further study in WE-CAN 2018.

  8. A compact PTR-ToF-MS instrument for airborne measurements of volatile organic compounds at high spatiotemporal resolution

    Directory of Open Access Journals (Sweden)

    M. Müller

    2014-11-01

    Full Text Available Herein, we report on the development of a compact proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS for airborne measurements of volatile organic compounds (VOCs. The new instrument resolves isobaric ions with a mass resolving power (m/Δm of ~1000, provides accurate m/z measurements (Δm < 3 mDa, records full mass spectra at 1 Hz and thus overcomes some of the major analytical deficiencies of quadrupole-MS-based airborne instruments. 1 Hz detection limits for biogenic VOCs (isoprene, α total monoterpenes, aromatic VOCs (benzene, toluene, xylenes and ketones (acetone, methyl ethyl ketone range from 0.05 to 0.12 ppbV, making the instrument well-suited for fast measurements of abundant VOCs in the continental boundary layer. The instrument detects and quantifies VOCs in locally confined plumes (< 1 km, which improves our capability of characterizing emission sources and atmospheric processing within plumes. A deployment during the NASA 2013 DISCOVER-AQ mission generated high vertical- and horizontal-resolution in situ data of VOCs and ammonia for the validation of satellite retrievals and chemistry transport models.

  9. Eddy covariance VOC emission and deposition fluxes above grassland using PTR-TOF

    Directory of Open Access Journals (Sweden)

    T. M. Ruuskanen

    2011-01-01

    Full Text Available Eddy covariance (EC is the preferable technique for flux measurements since it is the only direct flux determination method. It requires a continuum of high time resolution measurements (e.g. 5–20 Hz. For volatile organic compounds (VOC soft ionization via proton transfer reaction has proven to be a quantitative method for real time mass spectrometry; here we use a proton transfer reaction time of flight mass spectrometer (PTR-TOF for 10 Hz EC measurements of full mass spectra up to m/z 315. The mass resolution of the PTR-TOF enabled the identification of chemical formulas and separation of oxygenated and hydrocarbon species exhibiting the same nominal mass. We determined 481 ion mass peaks from ambient air concentration above a managed, temperate mountain grassland in Neustift, Stubai Valley, Austria. During harvesting we found significant fluxes of 18 compounds distributed over 43 ions, including protonated parent compounds, as well as their isotopes and fragments and VOC-H+ – water clusters. The dominant BVOC fluxes were methanol, acetaldehyde, ethanol, hexenal and other C6 leaf wound compounds, acetone, acetic acid, monoterpenes and sequiterpenes.

    The smallest reliable fluxes we determined were less than 0.1 nmol m−2 s−1, as in the case of sesquiterpene emissions from freshly cut grass. Terpenoids, including mono- and sesquiterpenes, were also deposited to the grassland before and after the harvesting. During cutting, total VOC emission fluxes up to 200 nmolC m−2 s−1 were measured. Methanol emissions accounted for half of the emissions of oxygenated VOCs and a third of the carbon of all measured VOC emissions during harvesting.

  10. Analysis of trace gases at ppb levels by proton transfer reaction mass spectrometry (PTR-MS)

    International Nuclear Information System (INIS)

    Lindinger, W.; Hansel, A.

    1996-01-01

    A proton transfer reaction mass spectrometry (PTR-MS) system has been developed which allows for on-line measurements of trace gas components with concentrations as low as 1 ppb. The method is based on reactions of H 3 O + ions, which perform non-dissociative proton transfer to most of the common organic trace constituents but do not react with any of the components present in clean air. Examples of medical information obtained by means of breath analysis, of environmental trace analysis, and examples in the field of food chemistry demonstrate the wide applicability of the method. (Authors)

  11. Investigation of Volatiles Emitted from Freshly Cut Onions (Allium cepa L. by Real Time Proton-Transfer Reaction-Mass Spectrometry (PTR-MS

    Directory of Open Access Journals (Sweden)

    Mette Marie Løkke

    2012-11-01

    Full Text Available Volatile organic compounds (VOCs in cut onions (Allium cepa L. were continuously measured by PTR-MS during the first 120 min after cutting. The headspace composition changed rapidly due to the very reactive volatile sulfurous compounds emitted from onion tissue after cell disruption. Mass spectral signals corresponding to propanethial S-oxide (the lachrymatory factor and breakdown products of this compound dominated 0–10 min after cutting. Subsequently, propanethiol and dipropyl disulfide predominantly appeared, together with traces of thiosulfinates. The concentrations of these compounds reached a maximum at 60 min after cutting. Propanethiol was present in highest concentrations and had an odor activity value 20 times higher than dipropyl disulfide. Thus, propanethiol is suggested to be the main source of the characteristic onion odor. Monitoring the rapid changes of VOCs in the headspace of cut onion necessitates a high time resolution, and PTR-MS is demonstrated to be a very suitable method for monitoring the headspace of freshly cut onions directly after cutting without extraction or pre-concentration.

  12. Observations of VOC emissions and photochemical products over US oil- and gas-producing regions using high-resolution H3O+ CIMS (PTR-ToF-MS

    Directory of Open Access Journals (Sweden)

    A. Koss

    2017-08-01

    Full Text Available VOCs related to oil and gas extraction operations in the United States were measured by H3O+ chemical ionization time-of-flight mass spectrometry (H3O+ ToF-CIMS/PTR-ToF-MS from aircraft during the Shale Oil and Natural Gas Nexus (SONGNEX campaign in March–April 2015. This work presents an overview of major VOC species measured in nine oil- and gas-producing regions, and a more detailed analysis of H3O+ ToF-CIMS measurements in the Permian Basin within Texas and New Mexico. Mass spectra are dominated by small photochemically produced oxygenates and compounds typically found in crude oil: aromatics, cyclic alkanes, and alkanes. Mixing ratios of aromatics were frequently as high as those measured downwind of large urban areas. In the Permian, the H3O+ ToF-CIMS measured a number of underexplored or previously unreported species, including aromatic and cycloalkane oxidation products, nitrogen heterocycles including pyrrole (C4H5N and pyrroline (C4H7N, H2S, and a diamondoid (adamantane or unusual monoterpene. We additionally assess the specificity of a number of ion masses resulting from H3O+ ion chemistry previously reported in the literature, including several new or alternate interpretations.

  13. Observations of VOC emissions and photochemical products over US oil- and gas-producing regions using high-resolution H3O+ CIMS (PTR-ToF-MS)

    Science.gov (United States)

    Koss, Abigail; Yuan, Bin; Warneke, Carsten; Gilman, Jessica B.; Lerner, Brian M.; Veres, Patrick R.; Peischl, Jeff; Eilerman, Scott; Wild, Rob; Brown, Steven S.; Thompson, Chelsea R.; Ryerson, Thomas; Hanisco, Thomas; Wolfe, Glenn M.; St. Clair, Jason M.; Thayer, Mitchell; Keutsch, Frank N.; Murphy, Shane; de Gouw, Joost

    2017-08-01

    VOCs related to oil and gas extraction operations in the United States were measured by H3O+ chemical ionization time-of-flight mass spectrometry (H3O+ ToF-CIMS/PTR-ToF-MS) from aircraft during the Shale Oil and Natural Gas Nexus (SONGNEX) campaign in March-April 2015. This work presents an overview of major VOC species measured in nine oil- and gas-producing regions, and a more detailed analysis of H3O+ ToF-CIMS measurements in the Permian Basin within Texas and New Mexico. Mass spectra are dominated by small photochemically produced oxygenates and compounds typically found in crude oil: aromatics, cyclic alkanes, and alkanes. Mixing ratios of aromatics were frequently as high as those measured downwind of large urban areas. In the Permian, the H3O+ ToF-CIMS measured a number of underexplored or previously unreported species, including aromatic and cycloalkane oxidation products, nitrogen heterocycles including pyrrole (C4H5N) and pyrroline (C4H7N), H2S, and a diamondoid (adamantane) or unusual monoterpene. We additionally assess the specificity of a number of ion masses resulting from H3O+ ion chemistry previously reported in the literature, including several new or alternate interpretations.

  14. Emissions of volatile organic compounds inferred from airborne flux measurements over a megacity

    Directory of Open Access Journals (Sweden)

    T. Karl

    2009-01-01

    Full Text Available Toluene and benzene are used for assessing the ability to measure disjunct eddy covariance (DEC fluxes of Volatile Organic Compounds (VOC using Proton Transfer Reaction Mass Spectrometry (PTR-MS on aircraft. Statistically significant correlation between vertical wind speed and mixing ratios suggests that airborne VOC eddy covariance (EC flux measurements using PTR-MS are feasible. City-median midday toluene and benzene fluxes are calculated to be on the order of 14.1±4.0 mg/m2/h and 4.7±2.3 mg/m2/h, respectively. For comparison the adjusted CAM2004 emission inventory estimates toluene fluxes of 10 mg/m2/h along the footprint of the flight-track. Wavelet analysis of instantaneous toluene and benzene measurements during city overpasses is tested as a tool to assess surface emission heterogeneity. High toluene to benzene flux ratios above an industrial district (e.g. 10–15 g/g including the International airport (e.g. 3–5 g/g and a mean flux (concentration ratio of 3.2±0.5 g/g (3.9±0.3 g/g across Mexico City indicate that evaporative fuel and industrial emissions play an important role for the prevalence of aromatic compounds. Based on a tracer model, which was constrained by BTEX (BTEX– Benzene/Toluene/Ethylbenzene/m, p, o-Xylenes compound concentration ratios, the fuel marker methyl-tertiary-butyl-ether (MTBE and the biomass burning marker acetonitrile (CH3CN, we show that a combination of industrial, evaporative fuel, and exhaust emissions account for >87% of all BTEX sources. Our observations suggest that biomass burning emissions play a minor role for the abundance of BTEX compounds in the MCMA (2–13%.

  15. Experimental determination of the partitioning coefficient and volatility of important BVOC oxidation products using the Aerosol Collection Module (ACM) coupled to a PTR-ToF-MS

    Science.gov (United States)

    Gkatzelis, G.; Hohaus, T.; Tillmann, R.; Schmitt, S. H.; Yu, Z.; Schlag, P.; Wegener, R.; Kaminski, M.; Kiendler-Scharr, A.

    2015-12-01

    Atmospheric aerosol can alter the Earth's radiative budget and global climate but can also affect human health. A dominant contributor to the submicrometer particulate matter (PM) is organic aerosol (OA). OA can be either directly emitted through e.g. combustion processes (primary OA) or formed through the oxidation of organic gases (secondary organic aerosol, SOA). A detailed understanding of SOA formation is of importance as it constitutes a major contribution to the total OA. The partitioning between the gas and particle phase as well as the volatility of individual components of SOA is yet poorly understood adding uncertainties and thus complicating climate modelling. In this work, a new experimental methodology was used for compound-specific analysis of organic aerosol. The Aerosol Collection Module (ACM) is a newly developed instrument that deploys an aerodynamic lens to separate the gas and particle phase of an aerosol. The particle phase is directed to a cooled sampling surface. After collection particles are thermally desorbed and transferred to a detector for further analysis. In the present work, the ACM was coupled to a Proton Transfer Reaction-Time of Flight-Mass Spectrometer (PTR-ToF-MS) to detect and quantify organic compounds partitioning between the gas and particle phase. This experimental approach was used in a set of experiments at the atmosphere simulation chamber SAPHIR to investigate SOA formation. Ozone oxidation with subsequent photochemical aging of β-pinene, limonene and real plant emissions from Pinus sylvestris (Scots pine) were studied. Simultaneous measurement of the gas and particle phase using the ACM-PTR-ToF-MS allows to report partitioning coefficients of important BVOC oxidation products. Additionally, volatility trends and changes of the SOA with photochemical aging are investigated and compared for all systems studied.

  16. Real-time monitoring of emissions from monoethanolamine-based industrial scale carbon capture facilities.

    Science.gov (United States)

    Zhu, Liang; Schade, Gunnar Wolfgang; Nielsen, Claus Jørgen

    2013-12-17

    We demonstrate the capabilities and properties of using Proton Transfer Reaction time-of-flight mass spectrometry (PTR-ToF-MS) to real-time monitor gaseous emissions from industrial scale amine-based carbon capture processes. The benchmark monoethanolamine (MEA) was used as an example of amines needing to be monitored from carbon capture facilities, and to describe how the measurements may be influenced by potentially interfering species in CO2 absorber stack discharges. On the basis of known or expected emission compositions, we investigated the PTR-ToF-MS MEA response as a function of sample flow humidity, ammonia, and CO2 abundances, and show that all can exhibit interferences, thus making accurate amine measurements difficult. This warrants a proper sample pretreatment, and we show an example using a dilution with bottled zero air of 1:20 to 1:10 to monitor stack gas concentrations at the CO2 Technology Center Mongstad (TCM), Norway. Observed emissions included many expected chemical species, dominantly ammonia and acetaldehyde, but also two new species previously not reported but emitted in significant quantities. With respect to concerns regarding amine emissions, we show that accurate amine quantifications in the presence of water vapor, ammonia, and CO2 become feasible after proper sample dilution, thus making PTR-ToF-MS a viable technique to monitor future carbon capture facility emissions, without conventional laborious sample pretreatment.

  17. Long-term study of VOCs measured with PTR-MS at a rural site in New Hampshire with urban influences

    Directory of Open Access Journals (Sweden)

    R. Talbot

    2009-07-01

    Full Text Available A long-term, high time-resolution volatile organic compound (VOC data set from a ground site that experiences urban, rural, and marine influences in the Northeastern United States is presented. A proton-transfer-reaction mass spectrometer (PTR-MS was used to quantify 15 VOCs: a marine tracer dimethyl sulfide (DMS, a biomass burning tracer acetonitrile, biogenic compounds (monoterpenes, isoprene, oxygenated VOCs (OVOCs: methyl vinyl ketone (MVK plus methacrolein (MACR, methanol, acetone, methyl ethyl ketone (MEK, acetaldehyde, and acetic acid, and aromatic compounds (benzene, toluene, C8 and C9 aromatics. Time series, overall and seasonal medians, with 10th and 90th percentiles, seasonal mean diurnal profiles, and inter-annual comparisons of mean summer and winter diurnal profiles are shown. Methanol and acetone exhibit the highest overall median mixing ratios 1.44 and 1.02 ppbv, respectively. Comparing the mean diurnal profiles of less well understood compounds (e.g., MEK with better known compounds (e.g., isoprene, monoterpenes, and MVK + MACR that undergo various controls on their atmospheric mixing ratios provides insight into possible sources of the lesser known compounds. The constant diurnal value of ~0.7 for the toluene:benzene ratio in winter, may possibly indicate the influence of wood-based heating systems in this region. Methanol exhibits an initial early morning release in summer unlike any other OVOC (or isoprene and a dramatic late afternoon mixing ratio increase in spring. Although several of the OVOCs appear to have biogenic sources, differences in features observed between isoprene, methanol, acetone, acetaldehyde, and MEK suggest they are produced or emitted in unique ways.

  18. Analytical detection of explosives and illicit, prescribed and designer drugs using proton transfer reaction time-of-flight mass spectrometry (PTR-TOF-MS)

    Energy Technology Data Exchange (ETDEWEB)

    Agarwal, Bishu; Petersson, Fredrik; Juerschik, Simone [Institut fuer Ionenphysik und Angewandte Physik, Universitaet Innsbruck, Technikerstr. 25, 6020 Innsbruck (Austria); Sulzer, Philipp; Jordan, Alfons [IONICON Analytik GmbH, Eduard-Bodem-Gasse 3, 6020 Innsbruck (Austria); Maerk, Tilmann D. [Institut fuer Ionenphysik und Angewandte Physik, Universitaet Innsbruck, Technikerstr. 25, 6020 Innsbruck (Austria); IONICON Analytik GmbH, Eduard-Bodem-Gasse 3, 6020 Innsbruck (Austria); Watts, Peter; Mayhew, Chris A. [School of Physics and Astronomy, University of Birmingham, Edgbaston, Birmingham B15 4TT (United Kingdom)

    2011-07-01

    This work demonstrates the extremely favorable features of Proton Transfer Reaction Time-of-flight Mass Spectrometry (PTR-TOF-MS) for the detection and identification of solid explosives, chemical warfare agent simulants and illicit, prescribed and designer drugs in real time. Here, we report the use of PTR-TOF, for the detection of explosives (e.g., trinitrotoluene, trinitrobenzene) and illicit, prescribed and designer drugs (e.g., ecstasy, morphine, heroin, ethcathinone, 2C-D). For all substances, the protonated parent ion (as we used H{sub 3}O{sup +} as a reagent ion) could be detected, providing a high level of confidence in their identification since the high mass resolution allows compounds having the same nominal mass to be separated. We varied the E/N from 90 to 220 T{sub d} (1 T{sub d}=10{sup -17} Vcm{sup -1}). This allowed us to study fragmentation pathways as a function of E/N (reduced electric field). For a few compounds rather unusual E/N dependencies were also discovered.

  19. Unraveling the chemical complexity of biomass burning VOC emissions via H3O+ ToF-CIMS (PTR-ToF): emissions characterization

    Science.gov (United States)

    Koss, A.; Sekimoto, K.; Gilman, J.; Selimovic, V.; Coggon, M.; Zarzana, K. J.; Yuan, B.; Lerner, B. M.; Brown, S. S.; Jimenez, J. L.; Krechmer, J. E.; Warneke, C.; Yokelson, R. J.; De Gouw, J. A.

    2017-12-01

    Gas-phase biomass burning emissions can include hundreds, if not thousands, of unique volatile and intermediate-volatility organic compounds. It is crucial to know the composition of these emissions to understand secondary organic aerosol formation, ozone formation, and human health effects resulting from fires. However, the composition can vary greatly with fuel type and fire combustion process. During the FIREX 2016 laboratory intensive at the US Forest Service Fire Sciences Laboratory in Missoula, Montana, high-resolution H3O+-CIMS (PTR-ToF) was deployed to characterize VOC emissions. More than 500 ion masses were consistently enhanced in each of 58 fires, which included a wide variety of fuel types representative of the western United States. Using a combination of extensive literature review, H3O+ and NO+ CIMS with GC preseparation, comparison to other instruments, and mass spectral context, we were able to identify the VOC contributors to 90% of the instrument signal. This provides unprecedented chemical detail in high time resolution. We present chemical characteristics of emissions, including OH reactivity and volatility, and highlight areas where better identification is needed.

  20. Proton-transfer reaction mass spectrometry (PTR-MS) for the authentication of regionally unique South African lamb.

    Science.gov (United States)

    Erasmus, Sara W; Muller, Magdalena; Alewijn, Martin; Koot, Alex H; van Ruth, Saskia M; Hoffman, Louwrens C

    2017-10-15

    The volatile fingerprints of South African lamb meat and fat were measured by proton-transfer mass spectrometry (PTR-MS) to evaluate it as an authentication tool. Meat and fat of the Longissimus lumborum (LL) of lambs from six different regions were assessed. Analysis showed that the volatile fingerprints were affected by the origin of the meat. The classification of the origin of the lamb was achieved by examining the calculated and recorded fingerprints in combination with chemometrics. Four different partial least squares discriminant analysis (PLS-DA) models were fitted to the data to classify lamb meat and fat samples into "region of origin" (six different regions) and "origin" (Karoo vs. Non-Karoo). The estimation models classified samples 100% correctly. Validation of the first two models gave 42% (fat) and 58% (meat) correct classification of region, while the second two models performed better with 92% (fat) and 83% (meat) correct classification of origin. Copyright © 2017 Elsevier Ltd. All rights reserved.

  1. PTR, PCR and Energy Resolution Study of GAGG:Ce Scintillator

    Science.gov (United States)

    Limkitjaroenporn, Pruittipol; Hongtong, Wiraporn; Kim, Hong Joo; Kaewkhao, Jakrapong

    2018-03-01

    In this paper, the peak to total ratio (PTR), the peak to Compton ratio (PCR) and the energy resolution of cerium doped gadolinium aluminium gallium garnet (GAGG:Ce) scintillator are measured in the range of energy from 511 keV to 1332 keV using the radioactive source Na-22, Cs-137 and Co-60. The crystal is coupled with the PMT number R1306 and analyzed by the nuclear instrument module (NIM). The results found that the PTR and PCR of GAGG:Ce scintillator decrease with the increasing of energy. The results of energy resolution show the trend is decrease with the increasing of energy which corresponding to the higher energy resolution at higher energy. Moreover the energy resolution found to be linearly with.

  2. A comparison of new measurements of total monoterpene flux with improved measurements of speciated monoterpene flux

    Directory of Open Access Journals (Sweden)

    A. Lee

    2005-01-01

    Full Text Available Many monoterpenes have been identified in forest emissions using gas chromatography (GC. Until now, it has been impossible to determine whether all monoterpenes are appropriately measured using GC techniques. We used a proton transfer reaction mass spectrometer (PTR-MS coupled with the eddy covariance (EC technique to measure mixing ratios and fluxes of total monoterpenes above a ponderosa pine plantation. We compared PTR-MS-EC results with simultaneous measurements of eight speciated monoterpenes, β-pinene, α-pinene, 3-carene, d-limonene, β-phellandrene, α-terpinene, camphene, and terpinolene, made with an automated, in situ gas chromatograph with flame ionization detectors (GC-FID, coupled to a relaxed eddy accumulation system (REA. Monoterpene mixing ratios and fluxes measured by PTR-MS averaged 30±2.3% and 31±9.2% larger than by GC-FID, with larger mixing ratio discrepancies between the two techniques at night than during the day. Two unidentified peaks that correlated with β-pinene were resolved in the chromatograms and completely accounted for the daytime difference and reduced the nighttime mixing ratio difference to 20±2.9%. Measurements of total monoterpenes by PTR-MS-EC indicated that GC-FID-REA measured the common, longer-lived monoterpenes well, but that additional terpenes were emitted from the ecosystem that represented an important contribution to the total mixing ratio above the forest at night.

  3. Volatile organic compound emissions from the oil and natural gas industry in the Uinta Basin, Utah: point sources compared to ambient air composition

    OpenAIRE

    C. Warneke; F. Geiger; P. M. Edwards; W. Dube; G. Pétron; J. Kofler; A. Zahn; S. S. Brown; M. Graus; J. Gilman; B. Lerner; J. Peischl; T. B. Ryerson; J. A. de Gouw; J. M. Roberts

    2014-01-01

    The emissions of volatile organic compounds (VOCs) associated with oil and natural gas production in the Uinta Basin, Utah were measured at a ground site in Horse Pool and from a NOAA mobile laboratory with PTR-MS instruments. The VOC compositions in the vicinity of individual gas and oil wells and other point sources such as evaporation ponds, compressor stations and injection wells are compared to the measurements at Horse Pool. High mixing ratios of aroma...

  4. Field performance and identification capability of the Innsbruck PTR-TOF

    Science.gov (United States)

    Graus, M.; Müller, M.; Hansel, A.

    2009-04-01

    Over the last one and a half decades Proton Transfer Reaction Mass Spectrometry (PTR-MS) [1, 2] has gained recognition as fast on-line sensor for monitoring volatile organic compounds (VOC) in the atmosphere. Sample collection is very straight forward and the fact that no pre-concentration is needed is of particular advantage for compounds that are notoriously difficult to pre-concentrate and/or analyze by gas chromatographic (GC) methods. Its ionization method is very versatile, i.e. all compounds that perform exothermic proton transfer with hydronium ions - and most VOCs do so - are readily ionized, producing quasi-molecular ions VOC.H+. In the quasi-molecular ion the elemental composition of the analyte compound is conserved and allows, in combination with some background knowledge of the sample, conclusions about the identity of that compound. De Gouw and Warneke (2007) [3] summarized the applicability of PTR-MS in atmospheric chemistry but they also pointed out shortcomings in the identification capabilities. Goldstein and Galbally (2007) [4] addressed the multitude of VOCs potentially present in the atmosphere and they emphasized the gasphase-to-aerosol partitioning of organic compounds (volatile and semi-volatile) in dependence of carbon-chain length and oxygen containing functional groups. In collaboration with Ionicon and assisted by TOFWERK we developed a PTR time-of-flight (PTR-TOF) instrument that allows for the identification of the atomic composition of oxygenated hydrocarbons by exact-mass determination. A detection limit in the low pptv range was achieved at a time resolution of one minute, one-second detection limit is in the sub-ppbv range. In 2008 the Innsbruck PTR-TOF was field deployed in the icebreaker- and helicopter based Arctic Summer Cloud Ocean Study (ASCOS) to characterize the organic trace gas composition of the High Arctic atmosphere. During the six-week field campaign the PTR-TOF was run without problems even under harsh conditions in

  5. On-line detection of illicit substances in liquid phase with proton-transfer-reaction mass spectrometry (PTR-MS)

    Energy Technology Data Exchange (ETDEWEB)

    Juerschik, Simone; Agarwal, Bishu; Petersson, Fredrik [Institut fuer Ionenphysik und Angewandte Physik, Universitaet Innsbruck, Technikerstr. 25, 6020 Innsbruck (Austria); Sulzer, Philipp; Haidacher, Stefan; Jordan, Alfons; Schottkowsky, Ralf; Hartungen, Eugen; Hanel, Gernot; Seehauser, Hans; Maerk, Lukas [IONICON Analytik GmbH, Eduard-Bodem-Gasse 3, 6020 Innsbruck (Austria); Maerk, Tilmann D. [Institut fuer Ionenphysik und Angewandte Physik, Universitaet Innsbruck, Technikerstr. 25, 6020 Innsbruck (Austria); IONICON Analytik GmbH, Eduard-Bodem-Gasse 3, 6020 Innsbruck (Austria)

    2011-07-01

    The direct aqueous injection (DAI) technique was recently utilized for the detection of illicit substances in liquid phase. DAI turns out to be an ideal solution for direct analysis of liquid samples, since we can make good use of the outstanding advantages, such as real-time analysis, no sample preparation, low detection limits and short response time. Differences in TNT concentration in the water could be seen dependent on time and original size of the pieces and we could demonstrate a linear correlation between the concentration in liquid and the PTR-MS signal. Furthermore, we were also able to demonstrate that this method is capable of detecting minute traces of ''rape drugs'', i.e. {gamma}-butyrolactone and 1,4-butanediol, in liquids. This new method achieving sensitivities in the around 100 pptw range appears therefore well suited for the fight against drug crime and terrorism and for the evaluation of contamination of ammunition dumping sites.

  6. A cell wall-bound anionic peroxidase, PtrPO21, is involved in lignin polymerization in Populus trichocarpa

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Chien-Yuan; Li, Quanzi; Tunlaya-Anukit, Sermsawat; Shi, Rui; Sun, Ying-Hsuan; Wang, Jack P.; Liu, Jie; Loziuk, Philip; Edmunds, Charles W.; Miller, Zachary D.; Peszlen, Ilona; Muddiman, David C.; Sederoff, Ronald R.; Chiang, Vincent L.

    2016-03-11

    Class III peroxidases are members of a large plant-specific sequence-heterogeneous protein family. Several sequence-conserved homologs have been associated with lignin polymerization in Arabidopsis thaliana, Oryza sativa, Nicotiana tabacum, Zinnia elegans, Picea abies, and Pinus sylvestris. In Populus trichocarpa, a model species for studies of wood formation, the peroxidases involved in lignin biosynthesis have not yet been identified. To do this, we retrieved sequences of all PtrPOs from Peroxibase and conducted RNA-seq to identify candidates. Transcripts from 42 PtrPOs were detected in stem differentiating xylem (SDX) and four of them are the most xylem-abundant (PtrPO12, PtrPO21, PtrPO42, and PtrPO64). PtrPO21 shows xylem-specific expression similar to that of genes encoding the monolignol biosynthetic enzymes. Using protein cleavage-isotope dilution mass spectrometry, PtrPO21 is detected only in the cell wall fraction and not in the soluble fraction. Downregulated transgenics of PtrPO21 have a lignin reduction of ~20% with subunit composition (S/G ratio) similar to wild type. The transgenics show a growth reduction and reddish color of stem wood. The modulus of elasticity (MOE) of the stems of the downregulated PtrPO21-line 8 can be reduced to ~60% of wild type. Differentially expressed gene (DEG) analysis of PtrPO21 downregulated transgenics identified a significant overexpression of PtPrx35, suggesting a compensatory effect within the peroxidase family. No significant changes in the expression of the 49 P. trichocarpa laccases (PtrLACs) were observed.

  7. Isotope ratio monitoring LC/MS (IRM-LC/MS): new applications

    International Nuclear Information System (INIS)

    Juchelka, D; Hilkert, A.; Krummen, M.

    2005-01-01

    With the introduction of compound specific isotope analysis by isotope ratio monitoring GC/ MS (IRM-GC/MS) the immediate demand for similar applications using HPLC was created. Many compounds of biological, medical, pharmaceutical and environmental interest are not volatile or too polar. Consequently, they cannot be directly analyzed by gas chromatography. In IRM-GC/MS the carrier is helium, which does not interfere with the essential combust ion step prior to isotope ratio mass spectrometry (IRMS). In opposite the LC mobile phase has inhibited a similar direct conversion up to now. All earlier IRM-LC/MS approaches were based on the removal of the liquid phase prior to combustion risking fractionation of the isotope ratios of the eluted compounds. To avoid such restrictions we developed a new continuous flow concept for the coupling of an HPLC system to the isotope ratio MS for 13 C/ 12C isotope ratio analysis. In the Finnigan LC IsoLink, the liquid phase is not removed from the sample prior to oxidation. The sample is oxidized still in the mobile phase followed by on-line separation of the CO 2 from the liquid phase and transfer into the isotope ratio MS. Therefore, this strategy is based on water and inorganic buffers as mobile phase. The new approach opens up a whole new world in the application of gas isotope ratio mass spectrometry. The 13 C/ 12 C ratio s of organic acids, amino acids, carbohydrates and nucleotides can now be measured. These components typically within a complex matrix are separated by liquid chromatography followed by on-line determination of the isotope ratios. The draw backs of using derivatization and off-line preparation procedures can now be over come. This new technique allow s studying biochemical cycles, running tracer experiments and determining the origin of components. Applications from different scientific areas such as biogeochemistry, molecular biology, and pharmacy as well as authenticity control o f foods will be presented

  8. PTR-MS Characterization of VOCs Associated with Commercial Aromatic Bakery Yeasts of Wine and Beer Origin

    Directory of Open Access Journals (Sweden)

    Vittorio Capozzi

    2016-04-01

    Full Text Available In light of the increasing attention towards “green” solutions to improve food quality, the use of aromatic-enhancing microorganisms offers the advantage to be a natural and sustainable solution that did not negatively influence the list of ingredients. In this study, we characterize, for the first time, volatile organic compounds (VOCs associated with aromatic bakery yeasts. Three commercial bakery starter cultures, respectively formulated with three Saccharomyces cerevisiae strains, isolated from white wine, red wine, and beer, were monitored by a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS, a direct injection analytical technique for detecting volatile organic compounds with high sensitivity (VOCs. Two ethanol-related peaks (m/z 65.059 and 75.080 described qualitative differences in fermentative performances. The release of compounds associated to the peaks at m/z 89.059, m/z 103.075, and m/z 117.093, tentatively identified as acetoin and esters, are coherent with claimed flavor properties of the investigated strains. We propose these mass peaks and their related fragments as biomarkers to optimize the aromatic performances of commercial preparations and for the rapid massive screening of yeast collections.

  9. Methanol and other VOC fluxes from a Danish beech forest during late springtime

    DEFF Research Database (Denmark)

    Schade, Gunnar W.; Solomon, Sheena J.; Dellwik, Ebba

    2011-01-01

    In-canopy mixing ratio gradients and above-canopy fluxes of several volatile organic compounds (VOCs) were measured using a commercial proton transfer reaction mass spectrometer (PTR-MS) in a European beech (Fagus sylvatica) forest in Denmark. Fluxes of methanol were bidirectional: Emission...

  10. Methyl chavicol: characterization of its biogenic emission rate, abundance, and oxidation products in the atmosphere

    Directory of Open Access Journals (Sweden)

    N. C. Bouvier-Brown

    2009-03-01

    Full Text Available We report measurements of ambient atmospheric mixing ratios for methyl chavicol and determine its biogenic emission rate. Methyl chavicol, a biogenic oxygenated aromatic compound, is abundant within and above Blodgett Forest, a ponderosa pine forest in the Sierra Nevada Mountains of California. Methyl chavicol was detected simultaneously by three in-situ instruments – a gas chromatograph with mass spectrometer detector (GC-MS, a proton transfer reaction mass spectrometer (PTR-MS, and a thermal desorption aerosol GC-MS (TAG – and found to be abundant within and above Blodgett Forest. Methyl chavicol atmospheric mixing ratios are strongly correlated with 2-methyl-3-buten-2-ol (MBO, a light- and temperature-dependent biogenic emission from the ponderosa pine trees at Blodgett Forest. Scaling from this correlation, methyl chavicol emissions account for 4–68% of the carbon mass emitted as MBO in the daytime, depending on the season. From this relationship, we estimate a daytime basal emission rate of 0.72–10.2 μgCg−1 h−1, depending on needle age and seasonality. We also present the first observations of its oxidation products (4-methoxybenzaldehyde and 4-methyoxy benzene acetaldehyde in the ambient atmosphere. Methyl chavicol is a major essential oil component of many plant species. This work suggests that methyl chavicol plays a significant role in the atmospheric chemistry of Blodgett Forest, and potentially other sites, and should be included explicitly in both biogenic volatile organic carbon emission and atmospheric chemistry models.

  11. Evaluation of an on-line methodology for measuring volatile organic compounds (VOC) fluxes by eddy-covariance with a PTR-TOF-Qi-MS

    Science.gov (United States)

    Loubet, Benjamin; Buysse, Pauline; Lafouge, Florence; Ciuraru, Raluca; Decuq, Céline; Zurfluh, Olivier

    2017-04-01

    Field scale flux measurements of volatile organic compounds (VOC) are essential for improving our knowledge of VOC emissions from ecosystems. Many VOCs are emitted from and deposited to ecosystems. Especially less known, are crops which represent more than 50% of French terrestrial surfaces. In this study, we evaluate a new on-line methodology for measuring VOC fluxes by Eddy Covariance with a PTR-Qi-TOF-MS. Measurements were performed at the ICOS FR-GRI site over a crop using a 30 m long high flow rate sampling line and an ultrasonic anemometer. A Labview program was specially designed for acquisition and on-line covariance calculation: Whole mass spectra ( 240000 channels) were acquired on-line at 10 Hz and stored in a temporary memory. Every 5 minutes, the spectra were mass-calibrated and normalized by the primary ion peak integral at 10 Hz. The mass spectra peaks were then retrieved from the 5-min averaged spectra by withdrawing the baseline, determining the resolution and using a multiple-peak detection algorithm. In order to optimize the peak detection algorithm for the covariance, we determined the covariances as the integrals of the peaks of the vertical-air-velocity-fluctuation weighed-averaged-spectra. In other terms, we calculate , were w is the vertical component of the air velocity, Sp is the spectra, t is time, lag is the decorrelation lag time and denotes an average. The lag time was determined as the decorrelation time between w and the primary ion (at mass 21.022) which integrates the contribution of all reactions of VOC and water with the primary ion. Our algorithm was evaluated by comparing the exchange velocity of water vapor measured by an open path absorption spectroscopy instrument and the water cluster measured with the PTRQi-TOF-MS. The influence of the algorithm parameters and lag determination is discussed. This study was supported by the ADEME-CORTEA COV3ER project (http://www6.inra.fr/cov3er).

  12. Measurements of VOC fluxes by dynamic plant and soil chambers in wheat and maize crop near Paris with a PTR-Qi-TOF-MS: Quantification and response to environmental and physiological drivers.

    Science.gov (United States)

    Gonzaga-Gomez, Lais; Boissard, Christophe; Ciuraru, Raluca; Lafouge, Florence; Zurfluh, Olivier; Buysse, Pauline; Decuq, Céline; Fanucci, Olivier; Gueudet, Jean-Christophe; Gros, Valérie; Sarda, Roland; Zannoni, Nora; Loubet, Benjamin

    2017-04-01

    Volatile organic compounds (VOC) play an important role in the chemistry of the atmosphere as precursors of secondary pollutants such as ozone and organic aerosols. A large variety of VOC are exchanged between plants (BVOC) and the atmosphere. Their fluxes are strongly dependent on environmental factors (temperature, light, biotic and abiotic stress) and vary greatly among plant species. Only few studies focused on BVOC emissions by agricultural plants and were mostly carried in North America. However, agricultural lands occupy 51% of the total country area in France, with wheat being one of the most important crop. We used a PTR-Qi-TOF-MS (national instrument within the ANAEE-France framework) and dynamic chambers to measure BVOC emissions from plant and soil compartments of a wheat and a maize crop near Paris (FR-GRI ICOS site). More than 700 masses were detected thanks to the resolution and sensitivity of this new instrument. We analyze the emission response to light, temperature and stomatal aperture in order to explain the mechanisms of BVOC exchanges by wheat plants. We investigate the emission differences between soil and plant compartment, and between wheat and maize crops. Acetone (m/z 59.049) was the predominant volatile compound in the emissions from wheat. Both methanol (m/z 33.033) and acetaldehyde (m/z 45.033) were also quite abundantly emitted but were less than half the acetone emissions. Other masses detected in relative importance in this study were m/z 63.026 (possible DMS), m/z 93.033 (not identified), m/z 69.069 (isoprene), m/z 57.069 (not identified), m/z 83.085 (possible green leaf volatiles), m/z 73.064 (methyl ethyl ketone). Their emissions were around 7 times smaller than the emissions of acetone. On the other hand we observed a deposition for, mainly, m/z 75.044 (hydroxyacetone) and m/z 61.028 (acetic acid). Methanol presented both positive and negative fluxes witch could indicate either emission or absorption of this compound by the

  13. Precise and accurate isotope ratio measurements by ICP-MS.

    Science.gov (United States)

    Becker, J S; Dietze, H J

    2000-09-01

    The precise and accurate determination of isotope ratios by inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS (LA-ICP-MS) is important for quite different application fields (e.g. for isotope ratio measurements of stable isotopes in nature, especially for the investigation of isotope variation in nature or age dating, for determining isotope ratios of radiogenic elements in the nuclear industry, quality assurance of fuel material, for reprocessing plants, nuclear material accounting and radioactive waste control, for tracer experiments using stable isotopes or long-lived radionuclides in biological or medical studies). Thermal ionization mass spectrometry (TIMS), which used to be the dominant analytical technique for precise isotope ratio measurements, is being increasingly replaced for isotope ratio measurements by ICP-MS due to its excellent sensitivity, precision and good accuracy. Instrumental progress in ICP-MS was achieved by the introduction of the collision cell interface in order to dissociate many disturbing argon-based molecular ions, thermalize the ions and neutralize the disturbing argon ions of plasma gas (Ar+). The application of the collision cell in ICP-QMS results in a higher ion transmission, improved sensitivity and better precision of isotope ratio measurements compared to quadrupole ICP-MS without the collision cell [e.g., for 235U/238U approximately 1 (10 microg x L(-1) uranium) 0.07% relative standard deviation (RSD) vs. 0.2% RSD in short-term measurements (n = 5)]. A significant instrumental improvement for ICP-MS is the multicollector device (MC-ICP-MS) in order to obtain a better precision of isotope ratio measurements (with a precision of up to 0.002%, RSD). CE- and HPLC-ICP-MS are used for the separation of isobaric interferences of long-lived radionuclides and stable isotopes by determination of spallation nuclide abundances in an irradiated tantalum target.

  14. Seasonality of isoprenoid emissions from a primary rainforest in central Amazonia

    Science.gov (United States)

    Alves, Eliane G.; Jardine, Kolby; Tota, Julio; Jardine, Angela; Yãnez-Serrano, Ana Maria; Karl, Thomas; Tavares, Julia; Nelson, Bruce; Gu, Dasa; Stavrakou, Trissevgeni; Martin, Scot; Artaxo, Paulo; Manzi, Antonio; Guenther, Alex

    2016-03-01

    Tropical rainforests are an important source of isoprenoid and other volatile organic compound (VOC) emissions to the atmosphere. The seasonal variation of these compounds is however still poorly understood. In this study, vertical profiles of mixing ratios of isoprene, total monoterpenes and total sesquiterpenes, were measured within and above the canopy, in a primary rainforest in central Amazonia, using a proton transfer reaction - mass spectrometer (PTR-MS). Fluxes of these compounds from the canopy into the atmosphere were estimated from PTR-MS measurements by using an inverse Lagrangian transport model. Measurements were carried out continuously from September 2010 to January 2011, encompassing the dry and wet seasons. Mixing ratios were higher during the dry (isoprene - 2.68 ± 0.9 ppbv, total monoterpenes - 0.67 ± 0.3 ppbv; total sesquiterpenes - 0.09 ± 0.07 ppbv) than the wet season (isoprene - 1.66 ± 0.9 ppbv, total monoterpenes - 0.47 ± 0.2 ppbv; total sesquiterpenes - 0.03 ± 0.02 ppbv) for all compounds. Ambient air temperature and photosynthetically active radiation (PAR) behaved similarly. Daytime isoprene and total monoterpene mixing ratios were highest within the canopy, rather than near the ground or above the canopy. By comparison, daytime total sesquiterpene mixing ratios were highest near the ground. Daytime fluxes varied significantly between seasons for all compounds. The maximums for isoprene (2.53 ± 0.5 µmol m-2 h-1) and total monoterpenes (1.77 ± 0.05 µmol m-2 h-1) were observed in the late dry season, whereas the maximum for total sesquiterpenes was found during the dry-to-wet transition season (0.77 ± 0.1 µmol m-2 h-1). These flux estimates suggest that the canopy is the main source of isoprenoids emitted into the atmosphere for all seasons. However, uncertainties in turbulence parameterization near the ground could affect estimates of fluxes that come from the ground. Leaf phenology seemed to be an important driver of seasonal

  15. Development of a novel methodology for indoor emission source identification

    DEFF Research Database (Denmark)

    Han, K.H.; Zhang, J.S.; Knudsen, H.N.

    2011-01-01

    The objective of this study was to develop and evaluate a methodology to identify individual sources of emissions based on the measurements of mixed air samples and the emission signatures of individual materials previously determined by Proton Transfer Reaction-Mass Spectrometry (PTR-MS), an on......-line analytical device. The methodology based on signal processing principles was developed by employing the method of multiple regression least squares (MRLS) and a normalization technique. Samples of nine typical building materials were tested individually and in combination, including carpet, ceiling material...... experiments and investigation are needed for cases where the relative emission rates among different compounds may change over a long-term period....

  16. A combined plant and reaction chamber setup to investigate the effect of pollution and UV-B radiation on biogenic emissions

    Science.gov (United States)

    Timkovsky, J.; Gankema, P.; Pierik, R.; Holzinger, R.

    2012-12-01

    Biogenic emissions account for almost 90% of total non-methane organic carbon emissions in the atmosphere. The goal of this project is to study the effect of pollution (ozone, NOx) and UV radiation on the emission of real plants. We have designed and built a setup where we combine plant chambers with a reaction chamber (75L volume) allowing the addition of pollutants at different locations. The main analytical tool is a PTR-TOF-MS instrument that can be optionally coupled with a GC system for improved compound identification. The setup is operational since March 2012 and first measurements indicate interesting results, three types of experiments will be presented: 1. Ozonolysis of b-pinene. In this experiment the reaction chamber was flushed with air containing b-pinene at approximate levels of 50 nmol/mol. After ~40 min b-pinene levels reached equilibrium in the reaction chamber and a constant supply of ozone was provided. Within 30 minutes this resulted in a 10 nmol/mol decrease of b-pinene levels in accordance with a reaction rate constant of 1.5*10-17 cm3molec-1s-1 and a residence time of 10 minutes in the reaction chamber. In addition we observed known oxidation products such as formaldehyde, acetone, and nopinone the molar yields of which were also in accordance with reported values. 2. Ozonolysis of biogenic emissions from tomato plants. The air containing the emissions from tomato plants was supplied to the reaction chamber. After adding ozone we observed the decrease of monoterpene concentrations inside the reaction chamber. The observed decrease is consistent for online PTR-MS and GC/PTR-MS measurements. Several ozonolysis products have been observed in the chamber. 3. The effect of UV-B radiation on biogenic emissions of tomato plants. Tomato plants were exposed to UV-B radiation and their emissions measured during and after the treatment. We observed significant changes in the emissions of volatile organic compounds, with specific compounds increasing

  17. Characterization of the ptr5+ gene involved in nuclear mRNA export in fission yeast

    International Nuclear Information System (INIS)

    Watanabe, Nobuyoshi; Ikeda, Terumasa; Mizuki, Fumitaka; Tani, Tokio

    2012-01-01

    Highlights: ► We cloned the ptr5 + gene involved in nuclear mRNA export in fission yeast. ► The ptr5 + gene was found to encode nucleoporin 85 (Nup85). ► Seh1p and Mlo3p are multi-copy suppressors for the ptr5 mutation. ► Ptr5p/Nup85p functions in nuclear mRNA export through the mRNA export factor Rae1p. ► Ptr5p/Nup85p interacts genetically with pre-mRNA splicing factors. -- Abstract: To analyze the mechanisms of mRNA export from the nucleus to the cytoplasm, we have isolated eleven mutants, ptr [poly(A) + RNA transport] 1 to 11, which accumulate poly(A) + RNA in the nucleus at a nonpermissive temperature in Schizosaccharomyces pombe. Of those, the ptr5–1 mutant shows dots- or a ring-like accumulation of poly(A) + RNA at the nuclear periphery after shifting to the nonpermissive temperature. We cloned the ptr5 + gene and found that it encodes a component of the nuclear pore complex (NPC), nucleoporin 85 (Nup85). The ptr5–1 mutant shows no defects in protein transport, suggesting the specific involvement of Ptr5p/Nup85p in nuclear mRNA export in S. pombe. We identified Seh1p, a nucleoporin interacting with Nup85p, an mRNA-binding protein Mlo3p, and Sac3p, a component of the TREX-2 complex involved in coupling of nuclear mRNA export with transcription, as multi-copy suppressors for the ptr5–1 mutation. In addition, we found that the ptr5–1 mutation is synthetically lethal with a mutation of the mRNA export factor Rae1p, and that the double mutant exaggerates defective nuclear mRNA export, suggesting that Ptr5p/Nup85p is involved in nuclear mRNA export through Rae1p. Interestingly, the ptr5–1 mutation also showed synthetic effects with several prp pre-mRNA splicing mutations, suggesting a functional linkage between the NPCs and the splicing apparatus in the yeast nucleus.

  18. An example of environmental applications of PTR-MS: characterization of pollution outflow from India and Arabia - biomass burning and fossil fuel combustion

    International Nuclear Information System (INIS)

    Wisthaler, A.; Hansel, A.; Stehr, J.W.; Dickerson, R.R.; Guazzotti, S.A.; Prather, K.A.

    2002-01-01

    Full text: One objective of the Indian Ocean Experiment (INDOEX 1999) was to characterize the chemical composition of pollution outflow from South Asia. Real-time single particle analysis (ATOFMS, Univ. of California- Riverside), CO analysis (Nondispersive Infrared Gas Filter Correlation Photometer, Univ. of Maryland) and fast-response VOC measurements (PTR-MS, Univ. of Innsbruck) measurements were performed onboard the NOAA R/V Ronald H. Brown. Gas phase and aerosol chemical composition of encountered air parcels changed according to their geographic origin traced by backtrajectory analysis (continental air from Arabia and India; maritime air). The relative strength of combustion related pollution sources (biomass burning (BB) vs. fossil fuel (FF) combustion) was determined from the relative abundance of different tracers: acetonitrile (BB), CO (BB and FF), submicron particles containing carbon but no potassium (FF), submicron particles containing carbon and potassium (BB and coal combustion), submicron particles containing carbon, potassium and lithium (coal combustion). Arabian air clearly reflected the signature of fossil fuel combustion, while air from the Indian subcontinent was strongly influenced by biomass burning. (author)

  19. Volatile Organic Compound (VOC) Emissions from Dairy Cows and Their Waste

    Science.gov (United States)

    Shaw, S.; Holzinger, R.; Mitloehner, F.; Goldstein, A.

    2005-12-01

    Biogenic VOCs are typically defined as those directly emitted from plants, but approximately 6% of global net primary production is consumed by cattle that carry out enteric fermentation and then emit VOCs that could also be considered biogenic. Current regulatory estimates suggest that dairy cattle in central California emit VOCs at rates comparable to those from passenger vehicles in the region, and thus contribute significantly to the extreme non-attainment of ozone standards there. We report PTR-MS measurements of ammonia and VOCs, and cavity-enhanced-absorption gas analyzer (Los Gatos Research, Inc.) measurements of CH4, emitted from dairy cattle in various stages of pregnancy/lactation and their waste. Experiments were conducted in chambers at UC Davis that simulate freestall cow housing conditions. CH4 fluxes ranged from 125-374 lb/cow/year. The compounds with the highest fluxes from '3 cows+waste' treatments were: ammonia (1-18), methanol (0-2.3), acetone+propanal (0.2-0.7), dimethylsulfide (0-0.4), and mass 109 (likely ID = p-cresol; 0-0.3) in lb/cow/year. Mass 60 (likely ID = trimethylamine) and acetic acid were also abundant. There were 10s of additional compounds with detectable, but small, emissions. A few compounds that were likely emitted (i.e. ethanol, formaldehyde, and dimethylamine) were not quantified by the PTR-MS. The total flux for all measured organic gases (TOG = CH4 + PTR-MS VOCs(including acetone+propanal)) averaged 246±45 lb/cow/year for '3 cows+waste' treatments, and was dominated by methane (>98%). TOG flux for 'waste only' treatments averaged 1.1±0.1 lb/cow/year, and was instead dominated by VOC (>84%). The PTR-MS VOCs as a percent of TOG (0.6±0.2%) emitted from '3 cows+waste' treatments in chamber conditions was a factor of 10 smaller than that currently estimated by the California Air Resources Board. In addition, the ozone forming potentials of the most abundant VOCs are only about 10% those of typical combustion or plant

  20. Heat Loss Testing of Schott's 2008 PTR70 Parabolic Trough Receiver

    Energy Technology Data Exchange (ETDEWEB)

    Burkholder, Frank [National Renewable Energy Lab. (NREL), Golden, CO (United States); Kutscher, Chuck [National Renewable Energy Lab. (NREL), Golden, CO (United States)

    2009-05-01

    Two Schott 2008 model year PTR70 HCEs were tested on NREL's heat loss test stand from 100 - 500 deg C in 50 deg C increments. Absorber emittance was determined from the laboratory testing so that the performance of the HCEs could be modeled in a parabolic trough collector. Collector/HCE simulation results for many different field operation conditions were used to create heat loss correlationcoefficients for Excelergy and SAM. SAM estimates that the decreased emittance of the 2008 PTR70 will decrease the LCOE for parabolic trough power plants by 0.5 cents/kWh and increase the electricity generated by 5% relative to previous PTR70s. These conclusions assume that the 2008 PTR70 is supplied at the same cost and with the same optical performance as earlier PTR70 models.

  1. Insight into the time-resolved extraction of aroma compounds during espresso coffee preparation: online monitoring by PTR-ToF-MS.

    Science.gov (United States)

    Sánchez-López, José A; Zimmermann, Ralf; Yeretzian, Chahan

    2014-12-02

    Using proton-transfer-reaction time-of-flight mass-spectrometry (PTR-ToF-MS), we investigated the extraction dynamic of 95 ion traces in real time (time resolution = 1 s) during espresso coffee preparation. Fifty-two of these ions were tentatively identified. This was achieved by online sampling of the volatile organic compounds (VOCs) in close vicinity to the coffee flow, at the exit of the extraction hose of the espresso machine (single serve capsules). Ten replicates of six different single serve coffee types were extracted to a final weight between 20-120 g, according to the recommended cup size of the respective coffee capsule (Ristretto, Espresso, and Lungo), and analyzed. The results revealed considerable differences in the extraction kinetics between compounds, which led to a fast evolution of the volatile profiles in the extract flow and consequently to an evolution of the final aroma balance in the cup. Besides exploring the time-resolved extraction dynamics of VOCs, the dynamic data also allowed the coffees types (capsules) to be distinguished from one another. Both hierarchical cluster analysis (HCA) and principal component analysis (PCA) showed full separation between the coffees types. The methodology developed provides a fast and simple means of studying the extraction dynamics of VOCs and differentiating between different coffee types.

  2. Characterization of the ptr5{sup +} gene involved in nuclear mRNA export in fission yeast

    Energy Technology Data Exchange (ETDEWEB)

    Watanabe, Nobuyoshi; Ikeda, Terumasa; Mizuki, Fumitaka [Department of Biological Sciences, Graduate School of Science and Technology, Kumamoto University, Kurokami, Kumamoto 860-8555 (Japan); Tani, Tokio, E-mail: ttani@sci.kumamoto-u.ac.jp [Department of Biological Sciences, Graduate School of Science and Technology, Kumamoto University, Kurokami, Kumamoto 860-8555 (Japan)

    2012-02-03

    Highlights: Black-Right-Pointing-Pointer We cloned the ptr5{sup +} gene involved in nuclear mRNA export in fission yeast. Black-Right-Pointing-Pointer The ptr5{sup +} gene was found to encode nucleoporin 85 (Nup85). Black-Right-Pointing-Pointer Seh1p and Mlo3p are multi-copy suppressors for the ptr5 mutation. Black-Right-Pointing-Pointer Ptr5p/Nup85p functions in nuclear mRNA export through the mRNA export factor Rae1p. Black-Right-Pointing-Pointer Ptr5p/Nup85p interacts genetically with pre-mRNA splicing factors. -- Abstract: To analyze the mechanisms of mRNA export from the nucleus to the cytoplasm, we have isolated eleven mutants, ptr [poly(A){sup +} RNA transport] 1 to 11, which accumulate poly(A){sup +} RNA in the nucleus at a nonpermissive temperature in Schizosaccharomyces pombe. Of those, the ptr5-1 mutant shows dots- or a ring-like accumulation of poly(A){sup +} RNA at the nuclear periphery after shifting to the nonpermissive temperature. We cloned the ptr5{sup +} gene and found that it encodes a component of the nuclear pore complex (NPC), nucleoporin 85 (Nup85). The ptr5-1 mutant shows no defects in protein transport, suggesting the specific involvement of Ptr5p/Nup85p in nuclear mRNA export in S. pombe. We identified Seh1p, a nucleoporin interacting with Nup85p, an mRNA-binding protein Mlo3p, and Sac3p, a component of the TREX-2 complex involved in coupling of nuclear mRNA export with transcription, as multi-copy suppressors for the ptr5-1 mutation. In addition, we found that the ptr5-1 mutation is synthetically lethal with a mutation of the mRNA export factor Rae1p, and that the double mutant exaggerates defective nuclear mRNA export, suggesting that Ptr5p/Nup85p is involved in nuclear mRNA export through Rae1p. Interestingly, the ptr5-1 mutation also showed synthetic effects with several prp pre-mRNA splicing mutations, suggesting a functional linkage between the NPCs and the splicing apparatus in the yeast nucleus.

  3. Seasonality of isoprenoid emissions from a primary rainforest in central Amazonia

    Directory of Open Access Journals (Sweden)

    E. G. Alves

    2016-03-01

    Full Text Available Tropical rainforests are an important source of isoprenoid and other volatile organic compound (VOC emissions to the atmosphere. The seasonal variation of these compounds is however still poorly understood. In this study, vertical profiles of mixing ratios of isoprene, total monoterpenes and total sesquiterpenes, were measured within and above the canopy, in a primary rainforest in central Amazonia, using a proton transfer reaction – mass spectrometer (PTR-MS. Fluxes of these compounds from the canopy into the atmosphere were estimated from PTR-MS measurements by using an inverse Lagrangian transport model. Measurements were carried out continuously from September 2010 to January 2011, encompassing the dry and wet seasons. Mixing ratios were higher during the dry (isoprene – 2.68 ± 0.9 ppbv, total monoterpenes – 0.67 ± 0.3 ppbv; total sesquiterpenes – 0.09 ± 0.07 ppbv than the wet season (isoprene – 1.66 ± 0.9 ppbv, total monoterpenes – 0.47 ± 0.2 ppbv; total sesquiterpenes – 0.03 ± 0.02 ppbv for all compounds. Ambient air temperature and photosynthetically active radiation (PAR behaved similarly. Daytime isoprene and total monoterpene mixing ratios were highest within the canopy, rather than near the ground or above the canopy. By comparison, daytime total sesquiterpene mixing ratios were highest near the ground. Daytime fluxes varied significantly between seasons for all compounds. The maximums for isoprene (2.53 ± 0.5 µmol m−2 h−1 and total monoterpenes (1.77 ± 0.05 µmol m−2 h−1 were observed in the late dry season, whereas the maximum for total sesquiterpenes was found during the dry-to-wet transition season (0.77 ± 0.1 µmol m−2 h−1. These flux estimates suggest that the canopy is the main source of isoprenoids emitted into the atmosphere for all seasons. However, uncertainties in turbulence parameterization near the ground could affect estimates of fluxes that come from the ground. Leaf

  4. Volatile organic compound emissions from the oil and natural gas industry in the Uintah Basin, Utah: oil and gas well pad emissions compared to ambient air composition

    Science.gov (United States)

    Warneke, C.; Geiger, F.; Edwards, P. M.; Dube, W.; Pétron, G.; Kofler, J.; Zahn, A.; Brown, S. S.; Graus, M.; Gilman, J. B.; Lerner, B. M.; Peischl, J.; Ryerson, T. B.; de Gouw, J. A.; Roberts, J. M.

    2014-10-01

    Emissions of volatile organic compounds (VOCs) associated with oil and natural gas production in the Uintah Basin, Utah were measured at a ground site in Horse Pool and from a NOAA mobile laboratory with PTR-MS instruments. The VOC compositions in the vicinity of individual gas and oil wells and other point sources such as evaporation ponds, compressor stations and injection wells are compared to the measurements at Horse Pool. High mixing ratios of aromatics, alkanes, cycloalkanes and methanol were observed for extended periods of time and for short-term spikes caused by local point sources. The mixing ratios during the time the mobile laboratory spent on the well pads were averaged. High mixing ratios were found close to all point sources, but gas well pads with collection and dehydration on the well pad were clearly associated with higher mixing ratios than other wells. The comparison of the VOC composition of the emissions from the oil and natural gas well pads showed that gas well pads without dehydration on the well pad compared well with the majority of the data at Horse Pool, and that oil well pads compared well with the rest of the ground site data. Oil well pads on average emit heavier compounds than gas well pads. The mobile laboratory measurements confirm the results from an emissions inventory: the main VOC source categories from individual point sources are dehydrators, oil and condensate tank flashing and pneumatic devices and pumps. Raw natural gas is emitted from the pneumatic devices and pumps and heavier VOC mixes from the tank flashings.

  5. Biogenic Volatile Organic Compound (BVOC) emissions from agricultural crop species: is guttation a possible source for methanol emissions following light/dark transition ?

    Science.gov (United States)

    Mozaffar, Ahsan; Amelynck, Crist; Bachy, Aurélie; Digrado, Anthony; Delaplace, Pierre; du Jardin, Patrick; Fauconnier, Marie-Laure; Schoon, Niels; Aubinet, Marc; Heinesch, Bernard

    2015-04-01

    In the framework of the CROSTVOC (CROp STress VOC) project, the exchange of biogenic volatile organic compounds (BVOCs) between two important agricultural crop species, maize and winter wheat, and the atmosphere has recently been measured during an entire growing season by using the eddy covariance technique. Because of the co-variation of BVOC emission drivers in field conditions, laboratory studies were initiated in an environmental chamber in order to disentangle the responses of the emissions to variations of the individual environmental parameters (such as PPFD and temperature) and to diverse abiotic stress factors. Young plants were enclosed in transparent all-Teflon dynamic enclosures (cuvettes) through which BVOC-free and RH-controlled air was sent. BVOC enriched air was subsequently sampled from the plant cuvettes and an empty cuvette (background) and analyzed for BVOCs in a high sensitivity Proton Transfer Reaction Mass Spectrometer (hs-PTR-MS) and for CO2 in a LI-7000 non-dispersive IR gas analyzer. Emissions were monitored at constant temperature (25 °C) and at a stepwise varying PPFD pattern (0-650 µmol m-2 s-1). For maize plants, sudden light/dark transitions at the end of the photoperiod were accompanied by prompt and considerable increases in methanol (m/z 33) and water vapor (m/z 39) emissions. Moreover, guttation droplets appeared on the sides and the tips of the leaves within a few minutes after light/dark transition. Therefore the assumption has been raised that methanol is also coming out with guttation fluid from the leaves. Consequently, guttation fluid was collected from young maize and wheat plants, injected in an empty enclosure and sampled by PTR-MS. Methanol and a large number of other compounds were observed from guttation fluid. Recent studies have shown that guttation from agricultural crops frequently occurs in field conditions. Further research is required to find out the source strength of methanol emissions by this guttation

  6. A plant chamber system with downstream reaction chamber to study the effects of pollution on biogenic emissions.

    Science.gov (United States)

    Timkovsky, J; Gankema, P; Pierik, R; Holzinger, R

    2014-01-01

    A system of two plant chambers and a downstream reaction chamber has been set up to investigate the emission of biogenic volatile organic compounds (BVOCs) and possible effects of pollutants such as ozone. The system can be used to compare BVOC emissions from two sets of differently treated plants, or to study the photochemistry of real plant emissions under polluted conditions without exposing the plants to pollutants. The main analytical tool is a proton-transfer-reaction time-of-flight mass spectrometer (PTR-TOF-MS) which allows online monitoring of biogenic emissions and chemical degradation products. The identification of BVOCs and their oxidation products is aided by cryogenic trapping and subsequent in situ gas chromatographic analysis.

  7. Astrobee Periodic Technical Review (PTR) Delta 3

    Science.gov (United States)

    Provencher, Christopher; Smith, Marion F.; Smith, Ernest Everett; Bualat, Maria Gabriele; Barlow, Jonathan Spencer

    2017-01-01

    Astrobee is a free flying robot for the inside of the International Space Station (ISS). The Periodic Technical Review (PTR) delta 3 is the final design review of the system presented to stakeholders.

  8. Sea-to-air flux of dimethyl sulfide in the South and North Pacific Ocean as measured by proton transfer reaction-mass spectrometry coupled with the gradient flux technique

    Science.gov (United States)

    Omori, Yuko; Tanimoto, Hiroshi; Inomata, Satoshi; Ikeda, Kohei; Iwata, Toru; Kameyama, Sohiko; Uematsu, Mitsuo; Gamo, Toshitaka; Ogawa, Hiroshi; Furuya, Ken

    2017-07-01

    Exchange of dimethyl sulfide (DMS) between the surface ocean and the lower atmosphere was examined by using proton transfer reaction-mass spectrometry coupled with the gradient flux (PTR-MS/GF) system. We deployed the PTR-MS/GF system and observed vertical gradients of atmospheric DMS just above the sea surface in the subtropical and transitional South Pacific Ocean and the subarctic North Pacific Ocean. In total, we obtained 370 in situ profiles, and of these we used 46 data sets to calculate the sea-to-air flux of DMS. The DMS flux determined was in the range from 1.9 to 31 μmol m-2 d-1 and increased with wind speed and biological activity, in reasonable accordance with previous observations in the open ocean. The gas transfer velocity of DMS derived from the PTR-MS/GF measurements was similar to either that of DMS determined by the eddy covariance technique or that of insoluble gases derived from the dual tracer experiments, depending on the observation sites located in different geographic regions. When atmospheric conditions were strongly stable during the daytime in the subtropical ocean, the PTR-MS/GF observations captured a daytime versus nighttime difference in DMS mixing ratios in the surface air overlying the ocean surface. The difference was mainly due to the sea-to-air DMS emissions and stable atmospheric conditions, thus affecting the gradient of DMS. This indicates that the DMS gradient is strongly controlled by diurnal variations in the vertical structure of the lower atmosphere above the ocean surface.

  9. Volatile organic compound mixing ratios above Beijing in November and December 2016

    Science.gov (United States)

    Acton, William; Shaw, Marvin; Huang, Zhonghui; Wang, Zhaoyi; Wang, Xinming; Zhang, Yanli; Davison, Brian; Langford, Ben; Mullinger, Neil; Nemitz, Eiko; Fu, Pingqing; Squires, Freya; Carpenter, Lucy; Lewis, Alastair; Hewitt, Nick

    2017-04-01

    Volatile organic compounds (VOCs) are emitted into the atmosphere from vegetation and anthropogenic sources such as fossil fuel combustion, biomass burning and the evaporation of petroleum products. These compounds play an important role in the chemistry of the lower atmosphere through secondary organic aerosol (SOA) formation and facilitating the formation of tropospheric ozone. As well as their indirect impact on human health via the formation of ozone and SOA, some VOCs, including benzene, directly affect human health adversely. Here we report VOC mixing ratios measured in Beijing during a 5 week intensive field campaign from the 7th November to the 10th December 2016. This work was carried out as part of the Sources and Emissions of Air Pollutants in Beijing (AIRPOLL-Beijing) work project within the Air Pollution and Human Health in a Developing Megacity (APHH-Beijing) research programme. APHH is a large multi-institutional study which aims to record the concentrations and identify the sources of urban air pollutants in Beijing, determine exposure, understand their effects on human health, and to identify solutions. VOC mixing ratios were recorded using a Proton Transfer Reaction-Time of Flight-Mass Spectrometer (PTR-ToF-MS, Ionicon Analytik) and a Selected Ion Flow Tube-Mass Spectrometer (SIFT-MS, SYFT Technologies). During the measurement period Beijing was subject to multiple pollution events that alternated with periods of relatively good air quality, allowing the VOCs within the polluted air masses to be identified and quantified. VOCs were sampled at 102 m with additional gradient measurements made at 3, 15, 32 and 64 m providing a vertical profile of VOC mixing ratios. Mixing ratios of methanol, acetonitrile, acetaldehyde, acetone, isoprene and aromatics species will be reported together with a discussion of potential sources. Comparisons will then be drawn with other large cities.

  10. Comparison of different real time VOC measurement techniques in a ponderosa pine forest

    Directory of Open Access Journals (Sweden)

    L. Kaser

    2013-03-01

    Full Text Available Volatile organic compound (VOC mixing ratios measured by five independent instruments are compared at a forested site dominated by ponderosa pine (Pinus Ponderosa during the BEACHON-ROCS field study in summer 2010. The instruments included a Proton Transfer Reaction Time of Flight Mass Spectrometer (PTR-TOF-MS, a Proton Transfer Reaction Quadrupole Mass Spectrometer (PTR-MS, a Fast Online Gas-Chromatograph coupled to a Mass Spectrometer (GC/MS; TOGA, a Thermal Dissociation Chemical Ionization Mass Spectrometer (PAN-CIMS and a Fiber Laser-Induced Fluorescence Instrument (FILIF. The species discussed in this comparison include the most important biogenic VOCs and a selected suite of oxygenated VOCs that are thought to dominate the VOC reactivity at this particular site as well as typical anthropogenic VOCs that showed low mixing ratios at this site. Good agreement was observed for methanol, the sum of the oxygenated hemiterpene 2-methyl-3-buten-2-ol (MBO and the hemiterpene isoprene, acetaldehyde, the sum of acetone and propanal, benzene and the sum of methyl ethyl ketone (MEK and butanal. Measurements of the above VOCs conducted by different instruments agree within 20%. The ability to differentiate the presence of toluene and cymene by PTR-TOF-MS is tested based on a comparison with GC-MS measurements, suggesting a study-average relative contribution of 74% for toluene and 26% for cymene. Similarly, 2-hydroxy-2-methylpropanal (HMPR is found to interfere with the sum of methyl vinyl ketone and methacrolein (MVK + MAC using PTR-(TOF-MS at this site. A study-average relative contribution of 85% for MVK + MAC and 15% for HMPR was determined. The sum of monoterpenes measured by PTR-MS and PTR-TOF-MS was generally 20–25% higher than the sum of speciated monoterpenes measured by TOGA, which included α-pinene, β-pinene, camphene, carene, myrcene, limonene, cineole as well as other terpenes. However, this difference is consistent throughout the study

  11. RNA interference regulates the cell cycle checkpoint through the RNA export factor, Ptr1, in fission yeast

    Energy Technology Data Exchange (ETDEWEB)

    Iida, Tetsushi, E-mail: tiida@nig.ac.jp [Division of Cytogenetics, National Institute of Genetics, Mishima, 1111 Yata, Mishima 411-8540 (Japan); The Graduate University for Advanced Studies, Sokendai, Mishima, 1111 Yata, Mishima 411-8540 (Japan); Precursory Research for Embryonic Science and Technology (PRESTO), Japan Science and Technology Agency (JST), 4-1-8, Honcho, Kawaguchi-shi, Saitama 332-0012 (Japan); Iida, Naoko [Division of Mutagenesis, National Institute of Genetics, Mishima, 1111 Yata, Mishima 411-8540 (Japan); Tsutsui, Yasuhiro [Department of Life Science, Graduate School of Bioscience and Biotechnology, Tokyo Institute of Technology, Nagatsuda-cho, Midori-ku, Yokohama 226-8501 (Japan); Yamao, Fumiaki [Division of Mutagenesis, National Institute of Genetics, Mishima, 1111 Yata, Mishima 411-8540 (Japan); The Graduate University for Advanced Studies, Sokendai, Mishima, 1111 Yata, Mishima 411-8540 (Japan); Kobayashi, Takehiko [Division of Cytogenetics, National Institute of Genetics, Mishima, 1111 Yata, Mishima 411-8540 (Japan); The Graduate University for Advanced Studies, Sokendai, Mishima, 1111 Yata, Mishima 411-8540 (Japan)

    2012-10-12

    Highlights: Black-Right-Pointing-Pointer RNAi is linked to the cell cycle checkpoint in fission yeast. Black-Right-Pointing-Pointer Ptr1 co-purifies with Ago1. Black-Right-Pointing-Pointer The ptr1-1 mutation impairs the checkpoint but does not affect gene silencing. Black-Right-Pointing-Pointer ago1{sup +} and ptr1{sup +} regulate the cell cycle checkpoint via the same pathway. Black-Right-Pointing-Pointer Mutations in ago1{sup +} and ptr1{sup +} lead to the nuclear accumulation of poly(A){sup +} RNAs. -- Abstract: Ago1, an effector protein of RNA interference (RNAi), regulates heterochromatin silencing and cell cycle arrest in fission yeast. However, the mechanism by which Ago1 controls cell cycle checkpoint following hydroxyurea (HU) treatment has not been elucidated. In this study, we show that Ago1 and other RNAi factors control cell cycle checkpoint following HU treatment via a mechanism independent of silencing. While silencing requires dcr1{sup +}, the overexpression of ago1{sup +} alleviated the cell cycle defect in dcr1{Delta}. Ago1 interacted with the mRNA export factor, Ptr1. The ptr1-1 mutation impaired cell cycle checkpoint but gene silencing was unaffected. Genetic analysis revealed that the regulation of cell cycle checkpoint by ago1{sup +} is dependent on ptr1{sup +}. Nuclear accumulation of poly(A){sup +} RNAs was detected in mutants of ago1{sup +} and ptr1{sup +}, suggesting there is a functional link between the cell cycle checkpoint and RNAi-mediated RNA quality control.

  12. Overexpression of PtrMYB119, a R2R3-MYB transcription factor from Populus trichocarpa, promotes anthocyanin production in hybrid poplar.

    Science.gov (United States)

    Cho, Jin-Seong; Nguyen, Van Phap; Jeon, Hyung-Woo; Kim, Min-Ha; Eom, Seok Hyun; Lim, You Jin; Kim, Won-Chan; Park, Eung-Jun; Choi, Young-Im; Ko, Jae-Heung

    2016-09-01

    Anthocyanins are a group of colorful and bioactive natural pigments with important physiological and ecological functions in plants. We found an MYB transcription factor (PtrMYB119) from Populus trichocarpa that positively regulates anthocyanin production when expressed under the control of the CaMV 35S promoter in transgenic Arabidopsis Amino acid sequence analysis revealed that PtrMYB119 is highly homologous to Arabidopsis PAP1 (PRODUCTION OF ANTHOCYANIN PIGMENT1), a well-known transcriptional activator of anthocyanin biosynthesis. Independently produced transgenic poplars overexpressing PtrMYB119 or PtrMYB120 (a paralogous gene to PtrMYB119) (i.e., 35S::PtrMYB119 and 35S::PtrMYB120, respectively) showed elevated accumulation of anthocyanins in the whole plants, including leaf, stem and even root tissues. Using a reverse-phase high-performance liquid chromatography, we confirmed that the majority of the accumulated anthocyanin in our transgenic poplar is cyanidin-3-O-glucoside. Gene expression analyses revealed that most of the genes involved in the anthocyanin biosynthetic pathway were highly upregulated in 35S::PtrMYB119 poplars compared with the nontransformed control poplar. Among these genes, expression of PtrCHS1 (Chalcone Synthase1) and PtrANS2 (Anthocyanin Synthase2), which catalyze the initial and last steps of anthocyanin biosynthesis, respectively, was upregulated by up to 350-fold. Subsequent transient activation assays confirmed that PtrMYB119 activated the transcription of both PtrCHS1 and PtrANS2 Interestingly, expression of MYB182, a repressor of both anthocyanin and proanthocyanidin (PA) biosynthesis, was largely suppressed in 35S::PtrMYB119 poplars, while expression of MYB134, an activator of PA biosynthesis, was not changed significantly. More interestingly, high-level accumulation of anthocyanins in 35S::PtrMYB119 poplars did not have an adverse effect on plant growth. Taken together, our results demonstrate that PtrMYB119 and PtrMYB120

  13. PtrWRKY73, a salicylic acid-inducible poplar WRKY transcription factor, is involved in disease resistance in Arabidopsis thaliana.

    Science.gov (United States)

    Duan, Yanjiao; Jiang, Yuanzhong; Ye, Shenglong; Karim, Abdul; Ling, Zhengyi; He, Yunqiu; Yang, Siqi; Luo, Keming

    2015-05-01

    A salicylic acid-inducible WRKY gene, PtrWRKY73, from Populus trichocarpa , was isolated and characterized. Overexpression of PtrWRKY73 in Arabidopsis thaliana increased resistance to biotrophic pathogens but reduced resistance against necrotrophic pathogens. WRKY transcription factors are commonly involved in plant defense responses. However, limited information is available about the roles of the WRKY genes in poplar defense. In this study, we isolated a salicylic acid (SA)-inducible WRKY gene, PtrWRKY73, from Populus trichocarpa, belonging to group I family and containing two WRKY domains, a D domain and an SP cluster. PtrWRKY73 was expressed predominantly in roots, old leaves, sprouts and stems, especially in phloem and its expression was induced in response to treatment with exogenous SA. PtrWRKY73 was localized to the nucleus of plant cells and exhibited transcriptional activation. Overexpression of PtrWRKY73 in Arabidopsis thaliana resulted in increased resistance to a virulent strain of the bacterial pathogen Pseudomonas syringae (PstDC3000), but more sensitivity to the necrotrophic fungal pathogen Botrytis cinerea. The SA-mediated defense-associated genes, such as PR1, PR2 and PAD4, were markedly up-regulated in transgenic plants overexpressing PtrWRKY73. Arabidopsis non-expressor of PR1 (NPR1) was not affected, whereas a defense-related gene PAL4 had reduced in PtrWRKY73 overexpressor plants. Together, these results indicated that PtrWRKY73 plays a positive role in plant resistance to biotrophic pathogens but a negative effect on resistance against necrotrophic pathogens.

  14. Regulation of Floral Terpenoid Emission and Biosynthesis in Sweet Basil (Ocimum basilicum).

    Science.gov (United States)

    Jiang, Yifan; Ye, Jiayan; Li, Shuai; Niinemets, Ülo

    2016-12-01

    Past studies have focused on the composition of essential oil of Ocimum basilicum leaves, but data on composition and regulation of its aerial emissions, especially floral volatile emissions are scarce. We studied the chemical profile, within-flower spatial distribution (sepals, petals, pistils with stamina and pedicels), diurnal emission kinetics and effects of exogenous methyl jasmonate (MeJA) application on the emission of floral volatiles by dynamic headspace collection and identification using gas chromatography-mass spectrometry (GC-MS) and proton transfer reaction mass spectrometry (PTR-MS). We observed more abundant floral emissions from flowers compared with leaves. Sepals were the main emitters of floral volatiles among the flower parts studied. The emissions of lipoxygenase compounds (LOX) and monoterpenoids, but not sesquiterpene emissions, displayed a diurnal variation driven by light. Response to exogenous MeJA treatment of flowers consisted of a rapid stress response and a longer-term acclimation response. The initial response was associated with enhanced emissions of fatty acid derivatives, monoterpenoids, and sesquiterpenoids without variation of the composition of individual compounds. The longer-term response was associated with enhanced monoterpenoid and sesquiterpenoid emissions with profound changes in the emission spectrum. According to correlated patterns of terpenoid emission changes upon stress, highlighted by a hierarchical cluster analysis, candidate terpenoid synthases responsible for observed diversity and complexity of released terpenoid blends were postulated. We conclude that flower volatile emissions differ quantitatively and qualitatively from leaf emissions, and overall contribute importantly to O. basilicum flavor, especially under stress conditions.

  15. Comparison of VOC measurements made by PTR-MS, adsorbent tubes-GC-FID-MS and DNPH derivatization-HPLC during the Sydney Particle Study, 2012: a contribution to the assessment of uncertainty in routine atmospheric VOC measurements

    Science.gov (United States)

    Dunne, Erin; Galbally, Ian E.; Cheng, Min; Selleck, Paul; Molloy, Suzie B.; Lawson, Sarah J.

    2018-01-01

    Understanding uncertainty is essential for utilizing atmospheric volatile organic compound (VOC) measurements in robust ways to develop atmospheric science. This study describes an inter-comparison of the VOC data, and the derived uncertainty estimates, measured with three independent techniques (PTR-MS, proton-transfer-reaction mass spectrometry; GC-FID-MS, gas chromatography with flame-ionization and mass spectrometric detection; and DNPH-HPLC, 2,4-dinitrophenylhydrazine derivatization followed by analysis by high-performance liquid chromatography) during routine monitoring as part of the Sydney Particle Study (SPS) campaign in 2012. Benzene, toluene, C8 aromatics, isoprene, formaldehyde and acetaldehyde were selected for the comparison, based on objective selection criteria from the available data. Bottom-up uncertainty analyses were undertaken for each compound and each measurement system. Top-down uncertainties were quantified via the inter-comparisons. In all seven comparisons, the correlations between independent measurement techniques were high with R2 values with a median of 0.92 (range 0.75-0.98) and small root mean square of the deviations (RMSD) of the observations from the regression line with a median of 0.11 (range 0.04-0.23 ppbv). These results give a high degree of confidence that for each comparison the response of the two independent techniques is dominated by the same constituents. The slope and intercept as determined by reduced major axis (RMA) regression gives a different story. The slopes varied considerably with a median of 1.25 and a range of 1.16-2.01. The intercepts varied with a median of 0.04 and a range of -0.03 to 0.31 ppbv. An ideal comparison would give a slope of 1.00 and an intercept of 0. Some sources of uncertainty that are poorly quantified by the bottom-up uncertainty analysis method were identified, including: contributions of non-target compounds to the measurement of the target compound for benzene, toluene and isoprene by

  16. Driving forces of individual BVOC emissions from a spruce tree in Central Germany; results from a dynamic enclosure study.

    Science.gov (United States)

    Bourtsoukidis, S.; Dittmann, A.; Jacobi, S.; Bonn, B.

    2012-04-01

    We have conducted seasonal ambient and emission measurements of a series of biogenic VOCs such as monoterpenes (MT), sesquiterpenes (SQT), isoprene, methanol, methyl chavicol and acetaldehyde. Therefore a plant enclosure technique was applied in order to investigate a Central European spruce forest and its emissions responses to meteorological and environmental parameters. A healthy ≈15m tall Norway spruce tree was selected and a vegetation enclosure technique was applied from April to November 2011. VOCs are measured by PTR-MS, while samples have also been analyzed with GC-MS (Gas Chromatography - Mass Spectrometry) techniques for intercomparison and identification of individual VOCs. E/N ratio was adjusted at 117Td[2] and the primary ion signal (H3O+) was continuously above 4×10^7cps, implying a high sensitivity to our measurements. Temperature, relative humidity, ozone, photosynthetic active radiation (PAR) and CO2 concentrations were continuously measured inside the plant cuvette. Meteorological and environmental parameters (radiation, atmospheric pressure, wind velocity, wind direction, temperature, O3, relative humidity, soil moisture, precipitation, global radiation, H2O, NO, NO2) were measured by HLUG (Hessian Agency for Environment and Geology) and DWD (German Weather Service), 50 meters away from the measuring site. In a peculiar season, which was characterized by a warm spring (temperature anomaly >40C), a wet summer (precipitation anomaly 126-150%) and an extremely dry autumn (precipitation anomaly monoterpene emission rate variability: model evaluations and sensitivity analyses, Journal of Geophysical Research., 98, 12609-12617, 1993.

  17. Atmospheric mixing ratios of methyl ethyl ketone (2-butanone in tropical, boreal, temperate and marine environments

    Directory of Open Access Journals (Sweden)

    A. M. Yáñez-Serrano

    2016-09-01

    Full Text Available Methyl ethyl ketone (MEK enters the atmosphere following direct emission from vegetation and anthropogenic activities, as well as being produced by the gas-phase oxidation of volatile organic compounds (VOCs such as n-butane. This study presents the first overview of ambient MEK measurements at six different locations, characteristic of forested, urban and marine environments. In order to understand better the occurrence and behaviour of MEK in the atmosphere, we analyse diel cycles of MEK mixing ratios, vertical profiles, ecosystem flux data, and HYSPLIT back trajectories, and compare with co-measured VOCs. MEK measurements were primarily conducted with proton-transfer-reaction mass spectrometer (PTR-MS instruments. Results from the sites under biogenic influence demonstrate that vegetation is an important source of MEK. The diel cycle of MEK follows that of ambient temperature and the forest structure plays an important role in air mixing. At such sites, a high correlation of MEK with acetone was observed (e.g. r2 = 0.96 for the SMEAR Estonia site in a remote hemiboreal forest in Tartumaa, Estonia, and r2 = 0.89 at the ATTO pristine tropical rainforest site in central Amazonia. Under polluted conditions, we observed strongly enhanced MEK mixing ratios. Overall, the MEK mixing ratios and flux data presented here indicate that both biogenic and anthropogenic sources contribute to its occurrence in the global atmosphere.

  18. Lead isotope ratio analysis of bullet samples by using quadrupole ICP-MS

    International Nuclear Information System (INIS)

    Tamura, Shu-ichi; Hokura, Akiko; Nakai, Izumi; Oishi, Masahiro

    2006-01-01

    The measurement conditions for the precise analysis of the lead stable isotope ratio by using an ICP-MS equipped with a quadrupole mass spectrometer were studied in order to apply the technique to the forensic identification of bullet samples. The values of the relative standard deviation obtained for the ratio of 208 Pb/ 206 Pb, 207 Pb/ 206 Pb and 204 Pb/ 206 Pb were lower than 0.2% after optimization of the analytical conditions, including the optimum lead concentration of the sample solution to be about 70 ppb and an integration time for 1 m/s of 15 s. This method was applied to an analysis of lead in bullets for rifles and handguns; a stable isotope ratio of lead was found to be suitable for the identification of bullets. This study has demonstrated that the lead isotope ratio measured by using a quadrupole ICP-MS was useful for a practical analysis of bullet samples in forensic science. (author)

  19. Comparison of VOC measurements made by PTR-MS, adsorbent tubes–GC-FID-MS and DNPH derivatization–HPLC during the Sydney Particle Study, 2012: a contribution to the assessment of uncertainty in routine atmospheric VOC measurements

    Directory of Open Access Journals (Sweden)

    E. Dunne

    2018-01-01

    Full Text Available Understanding uncertainty is essential for utilizing atmospheric volatile organic compound (VOC measurements in robust ways to develop atmospheric science. This study describes an inter-comparison of the VOC data, and the derived uncertainty estimates, measured with three independent techniques (PTR-MS, proton-transfer-reaction mass spectrometry; GC-FID-MS, gas chromatography with flame-ionization and mass spectrometric detection; and DNPH–HPLC, 2,4-dinitrophenylhydrazine derivatization followed by analysis by high-performance liquid chromatography during routine monitoring as part of the Sydney Particle Study (SPS campaign in 2012. Benzene, toluene, C8 aromatics, isoprene, formaldehyde and acetaldehyde were selected for the comparison, based on objective selection criteria from the available data. Bottom-up uncertainty analyses were undertaken for each compound and each measurement system. Top-down uncertainties were quantified via the inter-comparisons. In all seven comparisons, the correlations between independent measurement techniques were high with R2 values with a median of 0.92 (range 0.75–0.98 and small root mean square of the deviations (RMSD of the observations from the regression line with a median of 0.11 (range 0.04–0.23 ppbv. These results give a high degree of confidence that for each comparison the response of the two independent techniques is dominated by the same constituents. The slope and intercept as determined by reduced major axis (RMA regression gives a different story. The slopes varied considerably with a median of 1.25 and a range of 1.16–2.01. The intercepts varied with a median of 0.04 and a range of −0.03 to 0.31 ppbv. An ideal comparison would give a slope of 1.00 and an intercept of 0. Some sources of uncertainty that are poorly quantified by the bottom-up uncertainty analysis method were identified, including: contributions of non-target compounds to the measurement of the target compound for

  20. Regulation of Floral Terpenoid Emission and Biosynthesis in Sweet Basil (Ocimum basilicum)

    Science.gov (United States)

    Jiang, Yifan; Ye, Jiayan; Li, Shuai; Niinemets, Ülo

    2018-01-01

    Past studies have focused on the composition of essential oil of Ocimum basilicum leaves, but data on composition and regulation of its aerial emissions, especially floral volatile emissions are scarce. We studied the chemical profile, within-flower spatial distribution (sepals, petals, pistils with stamina and pedicels), diurnal emission kinetics and effects of exogenous methyl jasmonate (MeJA) application on the emission of floral volatiles by dynamic headspace collection and identification using gas chromatography-mass spectrometry (GC-MS) and proton transfer reaction mass spectrometry (PTR-MS). We observed more abundant floral emissions from flowers compared with leaves. Sepals were the main emitters of floral volatiles among the flower parts studied. The emissions of lipoxygenase compounds (LOX) and monoterpenoids, but not sesquiterpene emissions, displayed a diurnal variation driven by light. Response to exogenous MeJA treatment of flowers consisted of a rapid stress response and a longer-term acclimation response. The initial response was associated with enhanced emissions of fatty acid derivatives, monoterpenoids, and sesquiterpenoids without variation of the composition of individual compounds. The longer-term response was associated with enhanced monoterpenoid and sesquiterpenoid emissions with profound changes in the emission spectrum. According to correlated patterns of terpenoid emission changes upon stress, highlighted by a hierarchical cluster analysis, candidate terpenoid synthases responsible for observed diversity and complexity of released terpenoid blends were postulated. We conclude that flower volatile emissions differ quantitatively and qualitatively from leaf emissions, and overall contribute importantly to O. basilicum flavor, especially under stress conditions. PMID:29367803

  1. Temporal variability and sources of VOCs in urban areas of the eastern Mediterranean

    Directory of Open Access Journals (Sweden)

    C. Kaltsonoudis

    2016-11-01

    Full Text Available During the summer of 2012 volatile organic compounds (VOCs were monitored by proton transfer reaction mass spectrometry (PTR-MS in urban sites, in Athens and Patras, two of the largest cities in Greece. Also, during the winter of 2013, PTR-MS measurements were conducted in the center of the city of Athens. Positive matrix factorization (PMF was applied to the VOC measurements to gain insights about their sources. In summer most of the measured VOCs were due to biogenic and traffic emissions. Isoprene, monoterpenes, and several oxygenated VOCs (oVOCs originated mainly from vegetation either directly or as oxidation products. Isoprene average concentrations in Patras and Athens were 1 and 0.7 ppb respectively, while the monoterpene concentrations were 0.3 and 0.9 ppb respectively. Traffic was the main source of aromatic compounds during summer. For Patras and Athens the average concentrations of benzene were 0.1 and 0.2 ppb, of toluene 0.3 and 0.8 ppb, and of the xylenes 0.3 and 0.7 ppb respectively. Winter measurements in Athens revealed that biomass burning used for residential heating was a major VOC source contributing both aromatic VOCs and biogenic compounds such as monoterpenes. Several episodes related to biomass burning were identified and emission ratios (ERs and emission factors (EFs were estimated.

  2. Calibration and correction of LA-ICP-MS and LA-MC-ICP-MS analyses for element contents and isotopic ratios

    Directory of Open Access Journals (Sweden)

    Jie Lin

    2016-06-01

    Full Text Available LA-ICP-MS and LA-MC-ICP-MS have been the techniques of choice for achieving accurate and precise element content and isotopic ratio, the state-of-the-art technique combines the advantages of low detection limits with high spatial resolution, however, the analysis accuracy and precision are restricted by many factors, such as sensitivity drift, elemental/isotopic fractionation, matrix effects, interferences and the lack of sufficiently matrix-matched reference materials. Thus, rigorous and suitable calibration and correction methods are needed to obtain quantitative data. This review systematically summarized and evaluated the interference correction, quantitative calculation and sensitivity correction strategies in order to provide the analysts with suitable calibration and correction strategies according to the sample types and the analyzed elements. The functions and features of data reduction software ICPMSDataCal were also outlined, which can provide real-time and on-line data reduction of element content and isotopic ratios analyzed by LA-ICP-MS and LA-MC-ICP-MS.

  3. Volatile organic compound emissions from the oil and natural gas industry in the Uinta Basin, Utah: point sources compared to ambient air composition

    Science.gov (United States)

    Warneke, C.; Geiger, F.; Edwards, P. M.; Dube, W.; Pétron, G.; Kofler, J.; Zahn, A.; Brown, S. S.; Graus, M.; Gilman, J.; Lerner, B.; Peischl, J.; Ryerson, T. B.; de Gouw, J. A.; Roberts, J. M.

    2014-05-01

    The emissions of volatile organic compounds (VOCs) associated with oil and natural gas production in the Uinta Basin, Utah were measured at a ground site in Horse Pool and from a NOAA mobile laboratory with PTR-MS instruments. The VOC compositions in the vicinity of individual gas and oil wells and other point sources such as evaporation ponds, compressor stations and injection wells are compared to the measurements at Horse Pool. High mixing ratios of aromatics, alkanes, cycloalkanes and methanol were observed for extended periods of time and short-term spikes caused by local point sources. The mixing ratios during the time the mobile laboratory spent on the well pads were averaged. High mixing ratios were found close to all point sources, but gas wells using dry-gas collection, which means dehydration happens at the well, were clearly associated with higher mixing ratios than other wells. Another large source was the flowback pond near a recently hydraulically re-fractured gas well. The comparison of the VOC composition of the emissions from the oil and natural gas wells showed that wet gas collection wells compared well with the majority of the data at Horse Pool and that oil wells compared well with the rest of the ground site data. Oil wells on average emit heavier compounds than gas wells. The mobile laboratory measurements confirm the results from an emissions inventory: the main VOC source categories from individual point sources are dehydrators, oil and condensate tank flashing and pneumatic devices and pumps. Raw natural gas is emitted from the pneumatic devices and pumps and heavier VOC mixes from the tank flashings.

  4. Characterization of fresh and aged organic aerosol emissions from meat charbroiling

    Directory of Open Access Journals (Sweden)

    C. Kaltsonoudis

    2017-06-01

    Full Text Available Cooking emissions can be a significant source of fine particulate matter in urban areas. In this study the aerosol- and gas-phase emissions from meat charbroiling were characterized. Greek souvlakia with pork were cooked using a commercial charbroiler and a fraction of the emissions were introduced into a smog chamber where after a characterization phase they were exposed to UV illumination and oxidants. The particulate and gas phases were characterized by a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS and a proton-transfer-reaction mass spectrometer (PTR-MS correspondingly. More than 99 % of the aerosol emitted was composed of organic compounds, while black carbon (BC contributed 0.3 % and the inorganic species less than 0.5 % of the total aerosol mass. The initial O  :  C ratio was approximately 0.09 and increased up to 0.30 after a few hours of chemical aging (exposures of 1010 molecules cm−3 s for OH and 100 ppb h for ozone. The initial and aged AMS spectra differed considerably (θ =  27°. Ambient measurements were also conducted during Fat Thursday in Patras, Greece, when traditionally meat is charbroiled everywhere in the city. Positive matrix factorization (PMF revealed that cooking organic aerosol (COA reached up to 85 % of the total OA from 10:00 to 12:00 LST that day. The ambient COA factor in two major Greek cities had a mass spectrum during spring and summer similar to the aged meat charbroiling emissions. In contrast, the ambient COA factor during winter resembled strongly the fresh laboratory meat charbroiling emissions.

  5. Lead isotope ratios in lichen samples evaluated by ICP-ToF-MS to assess possible atmospheric pollution sources in Havana, Cuba.

    Science.gov (United States)

    Alvarez, Alfredo Montero; Estévez Alvarez, Juan R; do Nascimento, Clístenes Williams Araújo; González, Iván Pupo; Rizo, Oscar Díaz; Carzola, Lázaro Lima; Torres, Roberto Ayllón; Pascual, Jorge Gómez

    2017-01-01

    Epiphytic lichens, collected from 119 sampling sites grown over "Roistonea Royal Palm" trees, were used to assess the spatial distribution pattern of lead (Pb) and identify possible pollution sources in Havana (Cuba). Lead concentrations in lichens and topsoils were determined by flame atomic absorption spectrophotometry and inductively coupled plasma (ICP) atomic emission spectrometry, respectively, while Pb in crude oils and gasoline samples were measured by ICP-time of flight mass spectrometry (ICP-ToF-MS). Lead isotopic ratios measurements for lichens, soils, and crude oils were obtained by ICP-ToF-MS. We found that enrichment factors (EF) reflected a moderate contamination for 71% of the samples (EF > 10). The 206 Pb/ 207 Pb ratio values for lichens ranged from 1.17 to 1.20 and were a mixture of natural radiogenic and industrial activities (e.g., crude oils and fire plants). The low concentration of Pb found in gasoline (leaded gasoline is no longer used in Cuba.

  6. Assessing the role of "bottom-up" emissions and simplified chemical mechanisms in reconciling CESM2.0 with TOGA observations from the ORCAS and ATom-2 campaigns

    Science.gov (United States)

    Asher, E.; Emmons, L. K.; Kinnison, D. E.; Tilmes, S.; Hills, A. J.; Hornbrook, R. S.; Stephens, B. B.; Apel, E. C.

    2017-12-01

    Surface albedo and precipitation over the Southern Ocean are sensitive to parameterizations of aerosol formation and cloud dynamics in global climate models. Observations of precursor gases for natural aerosols can help constrain the uncertainty in these parameterizations, if used in conjunction with an appropriately simplified chemical mechanism. We implement current oceanic "bottom-up" emission climatologies of dimethyl sulfide (DMS) and isoprene in CESM2.0 (Lana et al. 2016; Archer et al. 2009) and compare modeled constituents from two separate chemical mechanisms with data obtained from the Trace Organic Gas Analyzer (TOGA) on the O2/N2 Ratios and CO2 Airborne Study in the Southern Ocean (ORCAS) and the Atmospheric Tomography Mission 2 (ATom-2). We use ORCAS measurements of DMS, isoprene, methyl vinyl ketone (MVK) and methacrolein (MACR) from over 10 flights in Jan. - Feb. 2016 as a training dataset to improve "bottom-up" emissions. Thereafter, we evaluate the scaled "top-down" emissions in CESM with TOGA data obtained from the Atmospheric Tomography Mission (ATom-2) in Feb. 2017. Recent laboratory studies at NCAR confirm that TOGA surpasses proton transfer reaction mass spectrometry (PTR-MS) and commercial gas chromatography (GC) instruments with respect to accurate measurements of oxygenated VOCs in low nitrogen oxide (NO) environments, such as MVK and MACR.

  7. Source Attribution of Methane Emissions in Northeastern Colorado Using Ammonia to Methane Emission Ratios

    Science.gov (United States)

    Eilerman, S. J.; Neuman, J. A.; Peischl, J.; Aikin, K. C.; Ryerson, T. B.; Perring, A. E.; Robinson, E. S.; Holloway, M.; Trainer, M.

    2015-12-01

    Due to recent advances in extraction technology, oil and natural gas extraction and processing in the Denver-Julesburg basin has increased substantially in the past decade. Northeastern Colorado is also home to over 250 concentrated animal feeding operations (CAFOs), capable of hosting over 2 million head of ruminant livestock (cattle and sheep). Because of methane's high Global Warming Potential, quantification and attribution of methane emissions from oil and gas development and agricultural activity are important for guiding greenhouse gas emission policy. However, due to the co-location of these different sources, top-down measurements of methane are often unable to attribute emissions to a specific source or sector. In this work, we evaluate the ammonia:methane emission ratio directly downwind of CAFOs using a mobile laboratory. Several CAFOs were chosen for periodic study over a 12-month period to identify diurnal and seasonal variation in the emission ratio as well as differences due to livestock type. Using this knowledge of the agricultural ammonia:methane emission ratio, aircraft measurements of ammonia and methane over oil and gas basins in the western US during the Shale Oil and Natural Gas Nexus (SONGNEX) field campaign in March and April 2015 can be used for source attribution of methane emissions.

  8. Characterization of polycyclic aromatic hydrocarbon emissions in the particulate and gas phase from smoldering mosquito coils containing various atomic hydrogen/carbon ratios

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Tzu-Ting, E-mail: d89844001@ntu.edu.tw [Department of Environmental Engineering and Health, Yuanpei University, No. 306, Yuanpei St., Hsin Chu 30015, Taiwan (China); Lin, Shaw-Tao [Department of Applied Chemistry, Providence University, No. 200 Chung-Chi Rd., Salu Dist., Taichung City 43301, Taiwan (China); Lin, Tser-Sheng [Department of Safety, Health, and Environmental Engineering, National United University, 2 Lien Da, Maioli 360, Taiwan (China); Chung, Hua-Yi [Department of Environmental Engineering and Health, Yuanpei University, No. 306, Yuanpei St., Hsin Chu 30015, Taiwan (China)

    2015-02-15

    The polycyclic aromatic hydrocarbon emissions in particulate and gas phases generated from smoldering mosquito coils containing various atomic H/C ratios were examined. Five types of mosquito coils were burned in a test chamber with a total airflow rate of 8.0 L/min at a constant relative humidity and temperature. The concentrations of individual PAHs were determined using the GC/MS technique. Among the used mosquito coils, the atomic H/C ratio ranged from 1.23 to 1.57, yielding total mass, gaseous, and particulate PAH emission factors of 28.17–78.72 mg/g, 26,139.80–35,932.98 and 5735.22–13,431.51 ng/g, respectively. The various partitions of PAHs in the gaseous and particulate phases were in the ranges, 70.26–83.70% and 16.30–29.74% for the utilized mosquito coils. The carcinogenic potency of PAH emissions in the particulate phase (203.82–797.76 ng/g) was approximately 6.92–25.08 times higher than that of the gaseous phase (26.27–36.07 ng/g). Based on the analyses of PAH emissions, mosquito coils containing the lowest H/C ratio, a low oxygen level, and additional additives (i.e., CaCO{sub 3}) are recommended for minimizing the production of total PAH emission factors and carcinogenic potency. - Highlights: • PAHs emissions are influenced by mosquito coils containing various atomic H/C ratios. • The PAHs generated by burning mosquito coils mainly occur in the gaseous phase. • Total TEQ emission factors of PAHs mainly consisted of the particulate phase (> 87%). • The BaP and BaA accounted for 71.13–77.28% of the total TEQ emission factors. • Special PAH ratios were regarded as characteristic ratios for burning mosquito coil.

  9. Overexpression of Poplar PtrWRKY89 in Transgenic Arabidopsis Leads to a Reduction of Disease Resistance by Regulating Defense-Related Genes in Salicylate- and Jasmonate-Dependent Signaling.

    Directory of Open Access Journals (Sweden)

    Yuanzhong Jiang

    Full Text Available The plant hormones jasmonic acid (JA and salicylic acid (SA play key roles in plant defenses against pathogens and several WRKY transcription factors have been shown to have a role in SA/JA crosstalk. In a previous study, overexpression of the poplar WRKY gene PtrWRKY89 enhanced resistance to pathogens in transgenic poplars. In this study, the promoter of PtrWRKY89 (ProPtrWRKY89 was isolated and used to drive GUS reporter gene. High GUS activity was observed in old leaves of transgenic Arabidopsis containing ProPtrWRKY89-GUS construct and GUS expression was extremely induced by SA solution and SA+MeJA mixture but not by MeJA treatment. Subcellular localization and transactivation assays showed that PtrWRKY89 acted as a transcription activator in the nucleus. Constitutive expression of PtrWRKY89 in Arabidopsis resulted in more susceptible to Pseudomonas syringae and Botrytis cinerea compared to wild-type plants. Quantitative real-time PCR (qRT-PCR analysis confirmed that marker genes of SA and JA pathways were down-regulated in transgenic Arabidopsis after pathogen inoculations. Overall, our results indicated that PtrWRKY89 modulates a cross talk in resistance to P. syringe and B. cinerea by negatively regulating both SA and JA pathways in Arabidopsis.

  10. Overexpression of Poplar PtrWRKY89 in Transgenic Arabidopsis Leads to a Reduction of Disease Resistance by Regulating Defense-Related Genes in Salicylate- and Jasmonate-Dependent Signaling.

    Science.gov (United States)

    Jiang, Yuanzhong; Guo, Li; Liu, Rui; Jiao, Bo; Zhao, Xin; Ling, Zhengyi; Luo, Keming

    2016-01-01

    The plant hormones jasmonic acid (JA) and salicylic acid (SA) play key roles in plant defenses against pathogens and several WRKY transcription factors have been shown to have a role in SA/JA crosstalk. In a previous study, overexpression of the poplar WRKY gene PtrWRKY89 enhanced resistance to pathogens in transgenic poplars. In this study, the promoter of PtrWRKY89 (ProPtrWRKY89) was isolated and used to drive GUS reporter gene. High GUS activity was observed in old leaves of transgenic Arabidopsis containing ProPtrWRKY89-GUS construct and GUS expression was extremely induced by SA solution and SA+MeJA mixture but not by MeJA treatment. Subcellular localization and transactivation assays showed that PtrWRKY89 acted as a transcription activator in the nucleus. Constitutive expression of PtrWRKY89 in Arabidopsis resulted in more susceptible to Pseudomonas syringae and Botrytis cinerea compared to wild-type plants. Quantitative real-time PCR (qRT-PCR) analysis confirmed that marker genes of SA and JA pathways were down-regulated in transgenic Arabidopsis after pathogen inoculations. Overall, our results indicated that PtrWRKY89 modulates a cross talk in resistance to P. syringe and B. cinerea by negatively regulating both SA and JA pathways in Arabidopsis.

  11. Emissions of hydrogen cyanide from on-road gasoline and diesel vehicles

    Science.gov (United States)

    Moussa, Samar G.; Leithead, Amy; Li, Shao-Meng; Chan, Tak W.; Wentzell, Jeremy J. B.; Stroud, Craig; Zhang, Junhua; Lee, Patrick; Lu, Gang; Brook, Jeffery R.; Hayden, Katherine; Narayan, Julie; Liggio, John

    2016-04-01

    Hydrogen cyanide (HCN) is considered a marker for biomass burning emissions and is a component of vehicle exhaust. Despite its potential health impacts, vehicular HCN emissions estimates and their contribution to regional budgets are highly uncertain. In the current study, Proton Transfer Reaction-Time of Flight-Mass Spectrometry (PTR-ToF-MS) was used to measure HCN emission factors from the exhaust of individual diesel, biodiesel and gasoline vehicles. Laboratory emissions data as a function of fuel type and driving mode were combined with ambient measurement data and model predictions. The results indicate that gasoline vehicles have the highest emissions of HCN (relative to diesel fuel) and that biodiesel fuel has the potential to significantly reduce HCN emissions even at realistic 5% blend levels. The data further demonstrate that gasoline direct injection (GDI) engines emit more HCN than their port fuel injection (PFI) counterparts, suggesting that the expected full transition of vehicle fleets to GDI will increase HCN emissions. Ambient measurements of HCN in a traffic dominated area of Toronto, Canada were strongly correlated to vehicle emission markers and consistent with regional air quality model predictions of ambient air HCN, indicating that vehicle emissions of HCN are the dominant source of exposure in urban areas. The results further indicate that additional work is required to quantify HCN emissions from the modern vehicle fleet, particularly in light of continuously changing engine, fuel and after-treatment technologies.

  12. Age estimation by pulp-to-tooth area ratio using cone-beam computed tomography: A preliminary analysis.

    Science.gov (United States)

    Rai, Arpita; Acharya, Ashith B; Naikmasur, Venkatesh G

    2016-01-01

    Age estimation of living or deceased individuals is an important aspect of forensic sciences. Conventionally, pulp-to-tooth area ratio (PTR) measured from periapical radiographs have been utilized as a nondestructive method of age estimation. Cone-beam computed tomography (CBCT) is a new method to acquire three-dimensional images of the teeth in living individuals. The present study investigated age estimation based on PTR of the maxillary canines measured in three planes obtained from CBCT image data. Sixty subjects aged 20-85 years were included in the study. For each tooth, mid-sagittal, mid-coronal, and three axial sections-cementoenamel junction (CEJ), one-fourth root level from CEJ, and mid-root-were assessed. PTR was calculated using AutoCAD software after outlining the pulp and tooth. All statistical analyses were performed using an SPSS 17.0 software program. Linear regression analysis showed that only PTR in axial plane at CEJ had significant age correlation ( r = 0.32; P < 0.05). This is probably because of clearer demarcation of pulp and tooth outline at this level.

  13. Estimate of anthropogenic halocarbon emission based on measured ratio relative to CO in the Pearl River Delta region, China

    Directory of Open Access Journals (Sweden)

    M. Shao

    2011-05-01

    Full Text Available Using a GC/FID/MS system, we analyzed the mixing ratio of 16 halocarbon species in more than 100 air samples collected in 2004 from the Pearl River Delta (PRD region of southern China. The results revealed that there are elevated mixing ratios for most of halocarbons, especially for HClC = CCl2 (trichloroethylene, TCE, CH2Cl2 (dichloromethane, DCM, CH3 Br (bromomethane, HCFC-22, CHCl3 (trichloromethane, CCl4 (tetrachloromethane, Cl2C = CCl2 (perchloroethylene, PCE, CH3CCl3 (methyl chloroform, MCF, and CFC-12. Comparisons were done with the data from TRACE-P and ALE/GAGE/AGAGE experiments, we found that the large variability in mixing ratios (relative standard deviation ranged from 9.31 % to 96.55 % of the halocarbons suggested substantial local emissions from the PRD region in 2004. Correlations between the mixing ratio of each species and carbon monoxide (CO was examined, and then the emission of each halocarbon was quantified based on scaling the optimized CO emission inventory with the slope of the regression line fitted to each species relative to CO. The calculated results revealed that mass of CH2Cl2 (7.0 Gg, CH3CCl3 (6.7 Gg, and Cl2C = CCl2 (2.3 Gg accounted for about 62.9 % of total halocarbon emissions, it suggested a significant contribution from solvent use in the PRD region. Emissions of HCFC-22 (3.5 Gg, an alternative refrigerant to chlorofluorocarbons (CFCs, were about 2.3 times greater than those of CFC-12 (1.6 Gg. CFC-12 and HCFC-22 accounted for 21.5 % of total emissions of halocarbons, so that the refrigerant would be the second largest source of halocarbons. However, the ratio approach found only minor emissions of CFCs, such as CFC-11, and the emission of CFC-114 and CFC-113 were close to zero. Emissions of other anthropogenic halocarbons, such as CCl

  14. SOA Formation Potential of Emissions from Soil and Leaf Litter

    Science.gov (United States)

    Faiola, C. L.; Vanderschelden, G. S.; Wen, M.; Cobos, D. R.; Jobson, B. T.; VanReken, T. M.

    2013-12-01

    In the United States, emissions of volatile organic compounds (VOCs) from natural sources exceed all anthropogenic sources combined. VOCs participate in oxidative chemistry in the atmosphere and impact the concentrations of ozone and particulate material. The formation of secondary organic aerosol (SOA) is particularly complex and is frequently underestimated using state-of-the-art modeling techniques. We present findings that suggest emissions of important SOA precursors from soil and leaf litter are higher than current inventories would suggest, particularly under conditions typical of Fall and Spring. Soil and leaf litter samples were collected at Big Meadow Creek from the University of Idaho Experimental Forest. The dominant tree species in this area of the forest are ponderosa pine, Douglas-fir, and western larch. Samples were transported to the laboratory and housed within a 0.9 cubic meter Teflon dynamic chamber where VOC emissions were continuously monitored with a GC-FID-MS and PTR-MS. Aerosol was generated from soil and leaf litter emissions by pumping the emissions into a 7 cubic meter Teflon aerosol growth chamber where they were oxidized with ozone in the absence of light. The evolution of particle microphysical and chemical characteristics was monitored over the following eight hours. Particle size distribution and chemical composition were measured with a SMPS and HR-ToF-AMS respectively. Monoterpenes dominated the emission profile with emission rates up to 283 micrograms carbon per meter squared per hour. The dominant monoterpenes emitted were beta-pinene, alpha-pinene, and delta-3-carene in descending order. The composition of the SOA produced was similar to biogenic SOA formed from oxidation of ponderosa pine emissions and alpha-pinene. Measured soil/litter monoterpene emission rates were compared with modeled canopy emissions. Results suggest that during fall and spring when tree emissions are lower, monoterpene emissions within forests may be

  15. Long-term measurements of biogenic VOCs in an Austrian valley - discussion of seasonal fluctuations of isoprene and monoterpene concentrations

    International Nuclear Information System (INIS)

    Dunkl, J.; Schnitzhofer, R.; Beauchamp, J.; Wisthaler, A; Hansel, A.

    2006-01-01

    Full text: A proton-transfer-reaction mass spectrometer (PTR-MS) was set up at a monitoring station in the river Inn valley (Vomp, Tirol, Austria) for a year-long measurement (February 2004-May 2005) of volatile organic compounds (VOCs) in the local valley air. Measurements of PM 10 , NO x and CO, and certain meteorological parameters were additionally made. Together, these data-sets enabled relationships between VOC abundances, meteorological conditions and anthropogenic emissions (primarily from automobile emissions) to be examined. The work presented here focuses on the biogenic VOCs measured under these real-world outdoor conditions. Initially, data needed to be separated between VOCs of anthropogenic and of biogenic origin. This was achieved by generating a model for the PTR-MS VOC data-set. A clear correlation between benzene and CO concentrations - indicating benzene's predominance from anthropogenic sources - allowed benzene to be used as a tracer for anthropogenic compounds. The model thus allowed a regression to be made whereby the maximum anthropogenic contributions of almost all VOCs could be established relative to benzene. The maximum contribution from biogenic emissions to each VOC could thus be determined as the difference between the total individual VOC signal and the corresponding maximum anthropogenic share. The two biogenic VOCs of principle interest here were isoprene and the monoterpenes (detected by PTR-MS at masses 69 amu and 137 amu, respectively). As expected, abundances of isoprene and the monoterpenes displayed a late-summer maximum (despite good vertical valley air dilution that acts to reduce VOC levels) when temperatures were high and sunlight hours long. Preliminary results will be presented and discussed. (author)

  16. Methyl jasmonate-induced emission of biogenic volatiles is biphasic in cucumber: a high-resolution analysis of dose dependence.

    Science.gov (United States)

    Jiang, Yifan; Ye, Jiayan; Li, Shuai; Niinemets, Ülo

    2017-07-20

    Methyl jasmonate (MeJA) is a key airborne elicitor activating jasmonate-dependent signaling pathways, including induction of stress-related volatile emissions, but how the magnitude and timing of these emissions scale with MeJA dose is not known. Treatments with exogenous MeJA concentrations ranging from mild (0.2 mM) to lethal (50 mM) were used to investigate quantitative relationships among MeJA dose and the kinetics and magnitude of volatile release in Cucumis sativus by combining high-resolution measurements with a proton-transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS) and GC-MS. The results highlighted biphasic kinetics of elicitation of volatiles. The early phase, peaking in 0.1-1 h after the MeJA treatment, was characterized by emissions of lipoxygenase (LOX) pathway volatiles and methanol. In the subsequent phase, starting in 6-12 h and reaching a maximum in 15-25 h after the treatment, secondary emissions of LOX compounds as well as emissions of monoterpenes and sesquiterpenes were elicited. For both phases, the maximum emission rates and total integrated emissions increased with applied MeJA concentration. Furthermore, the rates of induction and decay, and the duration of emission bursts were positively, and the timing of emission maxima were negatively associated with MeJA dose for LOX compounds and terpenoids, except for the duration of the first LOX burst. These results demonstrate major effects of MeJA dose on the kinetics and magnitude of volatile response, underscoring the importance of biotic stress severity in deciphering the downstream events of biological impacts. © The Author 2017. Published by Oxford University Press on behalf of the Society for Experimental Biology.

  17. In-core LOCA (PTR) analysis with poisoned moderator

    International Nuclear Information System (INIS)

    Kim, S. R.; Kim, B. G.; Kim, T. M.; Choi, J. H.; Kim, Yun Ho; Choi, Hoon

    2005-01-01

    CANDU reactors have been analyzed and evaluated for the postulated in-core LOCA while the reactor is operating normally with low moderator poison concentration. However, when the reactor is operating with relatively large amounts of boron and/or gadolinium poisons in the moderator, the assessment for fuel integrity was required for pressure tube rupture (PTR) accident. The methodology of in-core LOCA analysis with poisoned moderator is developed to determine the effective trip parameters, evaluate the fuel integrity, and establish the standard reactor start-up model for CANDU reactor recently. The developed methodology and results are presented

  18. Disjunct eddy covariance measurements of volatile organic compound fluxes using proton transfer reaction mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Taipale, R.

    2011-07-01

    Volatile organic compounds (VOCs) are emitted into the atmosphere from natural and anthropogenic sources, vegetation being the dominant source on a global scale. Some of these reactive compounds are deemed major contributors or inhibitors to aerosol particle formation and growth, thus making VOC measurements essential for current climate change research. This thesis discusses ecosystem scale VOC fluxes measured above a boreal Scots pine dominated forest in southern Finland. The flux measurements were performed using the micrometeorological disjunct eddy covariance (DEC) method combined with proton transfer reaction mass spectrometry (PTR-MS), which is an online technique for measuring VOC concentrations. The measurement, calibration, and calculation procedures developed in this work proved to be well suited to long-term VOC concentration and flux measurements with PTR-MS. A new averaging approach based on running averaged covariance functions improved the determination of the lag time between wind and concentration measurements, which is a common challenge in DEC when measuring fluxes near the detection limit. The ecosystem scale emissions of methanol, acetaldehyde, and acetone were substantial. These three oxygenated VOCs made up about half of the total emissions, with the rest comprised of monoterpenes. Contrary to the traditional assumption that monoterpene emissions from Scots pine originate mainly as evaporation from specialized storage pools, the DEC measurements indicated a significant contribution from de novo biosynthesis to the ecosystem scale monoterpene emissions. This thesis offers practical guidelines for long-term DEC measurements with PTR-MS. In particular, the new averaging approach to the lag time determination seems useful in the automation of DEC flux calculations. Seasonal variation in the monoterpene biosynthesis and the detailed structure of a revised hybrid algorithm, describing both de novo and pool emissions, should be determined in

  19. Membrane introduction proton-transfer-reaction mass spectrometry

    International Nuclear Information System (INIS)

    Alexander, M.; Boscaini, E.; Maerk, T.; Lindinger, W.

    2002-01-01

    Proton-transfer-reaction mass spectrometry (PTR-MS) is a rapidly expanding field with multiple applications in ion physics, atmospheric chemistry, food chemistry, volatile organic compounds monitoring and biology. Initial studies that combine PTR-MS and membrane introduction mass spectrometry (MIMS) were researched and outlined. First using PTR-MS, certain fundamental physical properties of a poly-dimethylsiloxane (PDMS) membrane including solubilities and diffusion coefficients were measured. Second, it was shown how the chemical selectivity of the (PDMS) can be used to extend the capabilities of the PTR-MS instrument by eliminating certain isobaric interferences and excluding water from volatile organic compounds (VOCs). Experiments with mixtures of several VOCs (toluene, benzene, acetone, propanal, methanol) are presented. (nevyjel)

  20. Plant-specific volatile organic compound emission rates from young and mature leaves of Mediterranean vegetation

    Science.gov (United States)

    Bracho-Nunez, Araceli; Welter, Saskia; Staudt, Michael; Kesselmeier, Jürgen

    2011-08-01

    The seasonality of vegetation, i.e., developmental stages and phenological processes, affects the emission of volatile organic compounds (VOCs). Despite the potential significance, the contributions of seasonality to VOC emission quality and quantity are not well understood and are therefore often ignored in emission simulations. We investigated the VOC emission patterns of young and mature leaves of several Mediterranean plant species in relation to their physiological and developmental changes during the growing period and estimated Es. Foliar emissions of isoprenoids and oxygenated VOCs like methanol and acetone were measured online by means of a proton transfer reaction mass spectrometer (PTR-MS) and offline with gas chromatography coupled with a mass spectrometer and flame ionization detector. The results suggest that VOC emission is a developmentally regulated process and that quantitative and qualitative variability is plant species specific. Leaf ontogeny clearly influenced both the VOC Es and the relative importance of different VOCs. Methanol was the major compound contributing to the sum of target VOC emissions in young leaves (11.8 ± 10.4 μg g-1 h-1), while its contribution was minor in mature leaves (4.1 ± 4.1 μg g-1 h-1). Several plant species showed a decrease or complete subsidence of monoterpene, sesquiterpene, and acetone emissions upon maturity, perhaps indicating a potential response to the higher defense demands of young emerging leaves.

  1. OVOC Emissions and Atmospheric Transformations.

    Science.gov (United States)

    Yokelson, R. J.; Christian, T. J.; Bertschi, I. T.; Ward, D. E.; Field, R. J.; Hobbs, P. V.; Goode, J.; Mason, S.; Susott, R.; Babbitt, R.; Hao, W. M.

    2002-12-01

    We quantified the main emissions from a few vegetation samples and many biomass fires using ground-based, open-path FTIR and airborne, closed-cell FTIR. The two instruments have been rigorously compared to each other and to PTR-MS and canister sampling. OVOC are major emissions from plants. OVOC account for about 70 percent of NMOC from savanna fires (the largest type of biomass burning) and 70-80 percent of NMOC from production and use of domestic biofuels (the second largest type of biomass burning). A table of average biofuel emissions is presented. Data from laboratory and free-burning fires, obtained from Alaska to South Africa, is used to develop equations that predict OVOC emissions from a wide variety of global fires. The impact of OVOC on smoke plume chemistry and the post-emission transformations of OVOC were investigated with two models. Addition of HCHO alone to the simple chemistry used in some global models dramatically reduces NOx lifetime and speeds up O3 formation rates in plumes. A detailed model verifies these effects and shows that OVOC profoundly affect formation of HOx, peroxide, and nitrogen reservoir species. The modeled photochemical transformations of OVOC are diverse, but some key pathways are unknown. We observed rapid production of both O3 and additional OVOC and OH of 1.7E7 in smoke plumes in Alaska and Africa; all reasonably consistent with model predictions. In addition, we found that cloud processing caused large post-emission changes in smoke trace gases including removal of nearly all methanol, a decrease in acetic acid, and a large increase in HCHO. These observations suggest that OVOC could react in cloud droplets and lead to production of modified aerosol. In addition, transport of OVOC by deep convection may be associated with large effects not explained by solubility alone.

  2. PtrWRKY19, a novel WRKY transcription factor, contributes to the regulation of pith secondary wall formation in Populus trichocarpa

    OpenAIRE

    Li Yang; Xin Zhao; Fan Yang; Di Fan; Yuanzhong Jiang; Keming Luo

    2016-01-01

    WRKY proteins are one of the largest transcription factor families in higher plants and play diverse roles in various biological processes. Previous studies have shown that some WRKY members act as negative regulators of secondary cell wall formation in pith parenchyma cells. However, the regulatory mechanism of pith secondary wall formation in tree species remains largely unknown. In this study, PtrWRKY19 encoding a homolog of Arabidopsis WRKY12 was isolated from Populus trichocarpa. PtrWRKY...

  3. Determination of stable isotope ratio of lead in airborne particulate matter by ICP-MS

    International Nuclear Information System (INIS)

    Mukai, Hitoshi; Ambe, Yoshinari

    1990-01-01

    ICP-MS was applied to the measurement of stable isotope ratios of lead, which are used as an indicator of the source of lead in airborne particulate matter. For the measurement of lead isotopes ratios, the influences of machine conditions, lead concentration and matrix elements to the precision and accuracy of the measurements were studied. At a scanning mode, dwell time of 40∼160 μs gave the best precision to the isotope ratio measurements; about 0.3 % of R.S.D. for 206 Pb/ 207 Pb and 206 Pb/ 208 Pb, 0.6 % for 206 Pb/ 204 Pb. Precision of the measurement was better at a high concentration of lead in sample solution. The observed value of 206 Pb/ 207 Pb ratio was not affected by the lead concentration, but in the cases of 206 Pb/ 204 Pb and 206 Pb/ 208 Pb, about 1 % of the value changed in the observed ratios with the lead concentration of 100∼500 μg/l. Six matrix elements (Na, K, Ca, Mg, Al, Fe) did not affect the observed isotope ratios up to 200 mg/l. The lead isotope ratios of reference materials {Urban Particulates (NIST) and Vehicle Exhausted Particulates (NIES)} were measured by using two kinds of sample; crude sample and lead-isolated sample from matrix elements by anodic deposition. Both cases gave the same isotope ratio values, therefore, lead isotope ratios in airborne particulate samples can be measured by ICP-MS without any separation of lead from matrix elements. (author)

  4. Isotope ratio measurements of uranium by LA-HR-ICP-MS

    Energy Technology Data Exchange (ETDEWEB)

    Marin, Rafael C.; Sarkis, Jorge E.S., E-mail: rafael.marin@usp.b, E-mail: jesarkis@ipen.b [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

    2011-07-01

    This work describes the utilization of Laser Ablation High Resolution Inductively Mass Spectrometry (LA-HR-ICP-MS) technique for the determination of uranium isotope composition in a UO{sub 2} pellet (CRM -125A) supplied and certified by the New Brunswick Laboratory (NBL). To carry out the adjustments of the parameters was used a glass standard NIST 610, supplied and certified by National Institute of Standards and Technology (NIST). The precision of the measurements were improved by adjusting the following parameters: RF power, laser beam diameter, defocusing of laser beam, laser energy, laser energy-density, auxiliary gas and sample gas. The measurements were performed on a continuous ablation with low energy density and defocusing, which demonstrated to be the optimum to reach the best signal stability. Isotope ratios, {sup 234}U/{sup 238}U, {sup 235}U/{sup 238}U and {sup 236}U/{sup 238}U were measured, reaching relative standard deviations (RSD) from 1.55% to 7.60%. The parameters which caused the greatest impact in order to improve the signal stability were RF power, defocusing and laser beam diameter. The results presented by the measurements revealed that the Laser ablation ICP-MS technique offers a rapid and accurate way to perform uranium isotope ratios without any sample preparation, since it allows carrying out the measurements straight on the sample, besides to preserve the testimony that is very important for safeguards and nuclear forensics purposes. (author)

  5. Emission ratio and isotopic signatures of molecular hydrogen emissions from tropical biomass burning

    Science.gov (United States)

    Haumann, F. A.; Batenburg, A. M.; Pieterse, G.; Gerbig, C.; Krol, M. C.; Röckmann, T.

    2013-09-01

    In this study, we identify a biomass-burning signal in molecular hydrogen (H2) over the Amazonian tropical rainforest. To quantify this signal, we measure the mixing ratios of H2 and several other species as well as the H2 isotopic composition in air samples that were collected in the BARCA (Balanço Atmosférico Regional de Carbono na Amazônia) aircraft campaign during the dry season. We derive a relative H2 emission ratio with respect to carbon monoxide (CO) of 0.31 ± 0.04 ppb ppb-1 and an isotopic source signature of -280 ± 41‰ in the air masses influenced by tropical biomass burning. In order to retrieve a clear source signal that is not influenced by the soil uptake of H2, we exclude samples from the atmospheric boundary layer. This procedure is supported by data from a global chemistry transport model. The ΔH2 / ΔCO emission ratio is significantly lower than some earlier estimates for the tropical rainforest. In addition, our results confirm the lower values of the previously conflicting estimates of the H2 isotopic source signature from biomass burning. These values for the emission ratio and isotopic source signatures of H2 from tropical biomass burning can be used in future bottom-up and top-down approaches aiming to constrain the strength of the biomass-burning source for H2. Hitherto, these two quantities relied only on combustion experiments or on statistical relations, since no direct signal had been obtained from in-situ observations.

  6. PAH diagnostic ratios for the identification of pollution emission sources

    International Nuclear Information System (INIS)

    Tobiszewski, Marek; Namieśnik, Jacek

    2012-01-01

    Polycyclic aromatic hydrocarbon (PAH) diagnostic ratios have recently come into common use as a tool for identifying and assessing pollution emission sources. Some diagnostic ratios are based on parent PAHs, others on the proportions of alkyl-substituted to non-substituted molecules. The ratios are applicable to PAHs determined in different environmental media: air (gas + particle phase), water, sediment, soil, as well as biomonitor organisms such as leaves or coniferous needles, and mussels. These ratios distinguish PAH pollution originating from petroleum products, petroleum combustion and biomass or coal burning. The compounds involved in each ratio have the same molar mass, so it is assumed they have similar physicochemical properties. Numerous studies show that diagnostic ratios change in value to different extents during phase transfers and environmental degradation. The paper reviews applications of diagnostic ratios, comments on their use and specifies their limitations. - Highlights: ► PAH diagnostic ratios may identify pollution coming from petroleum spills, fuel combustion and coal or biomass burning. ► They are sensitive to changes during PAHs environmental fate processes. ► Some diagnostic ratios are of limited value due to fast photodegradation of one of the compounds. - The paper reviews PAH diagnostic ratios that are applied to identify pollution emission originating from petroleum products, fuel combustion or coal and biomass burning.

  7. Use of Proton-Transfer-Reaction Mass Spectrometry to Characterize Volatile Organic Compound Sources at the La Porte Super Site During the Texas Air Quality Study 2000

    Energy Technology Data Exchange (ETDEWEB)

    Karl, Thomas G.; Jobson, B Tom T.; Kuster, W. C.; Williams, Eric; Stutz, Jochen P.; Shetter, Rick; Hall, Samual R.; Goldan, P. D.; Fehsenfeld, Fred C.; Lindinger, Werner

    2003-08-19

    Proton-transfer-reaction mass spectrometry (PTR-MS) was deployed for continuous real-time monitoring of volatile organic compounds (VOCs) at a site near the Houston Ship Channel during the Texas Air Quality Study 2000. Overall, 28 ions dominated the PTR-MS mass spectra and were assigned as anthropogenic aromatics (e.g., benzene, toluene, xylenes) and hydrocarbons (propene, isoprene), oxygenated compounds (e.g., formaldehyde, acetaldehyde, acetone, methanol, C7 carbonyls), and three nitrogencontaining compounds (e.g., HCN, acetonitrile and acrylonitrile). Biogenic VOCs were minor components at this site. Propene was the most abundant lightweight hydrocarbon detected by this technique with concentrations up to 100+ nmol mol-1, and was highly correlated with its oxidation products, formaldehyde (up to ~40 nmol mol-1) and acetaldehyde (up to ~80 nmol/mol), with typical ratios close to 1 in propene-dominated plumes. In the case of aromatic species the high time resolution of the obtained data set helped in identifying different anthropogenic sources (e.g., industrial from urban emissions) and testing current emission inventories. A comparison with results from complimentary techniques (gas chromatography, differential optical absorption spectroscopy) was used to assess the selectivity of this on-line technique in a complex urban and industrial VOC matrix and give an interpretation of mass scans obtained by ‘‘soft’’ chemical ionization using proton-transfer via H3O+. The method was especially valuable in monitoring rapidly changing VOC plumes which passed over the site, and when coupled with meteorological data it was possible to identify likely sources.

  8. Evaluating the effectiveness of joint emission control policies on the reduction of ambient VOCs: Implications from observation during the 2014 APEC summit in suburban Beijing

    Science.gov (United States)

    Li, Kun; Li, Junling; Wang, Weigang; Tong, Shengrui; Liggio, John; Ge, Maofa

    2017-09-01

    Ambient volatile organic compounds (VOCs) at a suburban Beijing site were on-line detected using proton transfer reaction-mass spectrometry (PTR-MS) during autumn of 2014, near the location of the Asia-Pacific Economic Cooperation (APEC) summit. During the APEC summit, the Chinese government enacted strict emission control policies. It was found that VOC concentrations only slightly decreased during the first emission control period (EC I), when control policies were performed in Beijing and 5 cities along the Tai-hang Mountains. However, most of the VOCs (10 out of 12 non-biogenic species) significantly decreased (more than 40%) during the second emission control period (EC II), when control policies were carried out in 16 cities including Beijing, Tianjin, 8 cities of Hebei province and 6 cities of Shandong province. Also the ratio of toluene and benzene decreased during EC II, likely because the emission control policies changed the proportions of different anthropogenic sources. Using the positive matrix factorization (PMF) source apportionment method, five factors are analyzed: (1) vehicle + fuel, (2) solvent, (3) biomass burning, (4) secondary, and (5) background + long-lived. Among them, vehicle + fuel, solvent and biomass burning contribute most of the VOCs concentrations (60%-80%) during the polluted periods and are affected most by emission control policies. During EC II, the reductions of vehicle + fuel, solvent, biomass burning and secondary species were all no less than 50%. Overall, when emission control policies were carried out in many North China Plain (NCP) cities (i.e. EC II), the VOC concentrations of suburban Beijing markedly decreased. This indicates the cross-regional joint-control policies have a large influence on reductions of organic gas species. The findings of this study have vital implications for helping formulate effective emission control policies in China and other countries.

  9. Concentrations and fluxes of biogenic volatile organic compounds above a Mediterranean macchia ecosystem in western Italy

    Directory of Open Access Journals (Sweden)

    B. Davison

    2009-08-01

    Full Text Available Emission rates and concentrations of biogenic volatile organic compounds (BVOCs were measured at a Mediterranean coastal site at Castelporziano, approximately 25 km south-west of Rome, between 7 May and 3 June 2007, as part of the ACCENT-VOCBAS field campaign on biosphere–atmosphere interactions. Concentrations and emission rates were measured using the disjunct eddy covariance (DEC method utilizing three different proton transfer reaction mass spectrometers (PTR-MS so allowing a comparison between the instruments. The high resolution data from the PTR-MS instruments considerably enhances the original BEMA measurements of the mid 1990s.

    Depending on the measurement period, the volume mixing ratios were in the range 1.6–3.5 ppbv for methanol, 0.44–1.3 ppbv for acetaldehyde, 0.96–2.1 ppbv for acetone, 0.10–0.14 ppbv for isoprene, and 0.13–0.30 ppbv for monoterpenes. A diurnal cycle in mixing ratios was apparent with daytime maxima for methanol, acetaldehyde, acetone, and isoprene. The fluxes ranged from 370–440 μg m−2 h−1 for methanol, 180–360 μg m−2 h−1 for acetaldehyde, 180–450 μg m−2 h−1 for acetone, 71–290 μg m−2 h−1 for isoprene, and 240–860 μg m−2 h−1 for monoterpenes. From the measured flux data (7 May–3 June an average basal emission rate for the Macchia vegetation was calculated of 430 μg m−2 h−1 for isoprene and 1100 μg m−2 h−1 for monoterpenes.

  10. Can Coronene and/or Benzo(a)pyrene/Coronene ratio act as unique markers for vehicle emission?

    International Nuclear Information System (INIS)

    Shen, Guofeng; Chen, Yuanchen; Wei, Siye; Fu, Xiaofang; Ding, Aijun; Wu, Haisuo; Tao, Shu

    2014-01-01

    Coronene is a high molecular weight polycyclic aromatic hydrocarbon with seven aromatic rings. It, more specifically a lower ratio of Benzo[a]pyrene to Coronone (BaP/COR), is suggested as a marker for vehicle emission. In the present study, emissions of Coronene were measured from residential combustions of wood, crop straw, and pellets. The detection of COR in non-vehicle emission sources, and comparable BaP/COR ratios between the solid fuel combustion and vehicle emissions indicated that the generality of COR or the BaP/COR ratio as markers for the vehicle emission would be questionable, especially for the area where solid fuel combustion dominated the PAHs emission. Highlights: • Coronene alone is not a unique marker for vehicle emission. • The specific ratio, BaP/Coronene, could be very high for gasoline emission. • The use of a specific ratio, BaP/Coronene, as a marker is debatable. -- Coronene alone is not a unique tracer for vehicle emission and the use of specific Benzo[a]pyrene to Coronene ratio needs more evaluation studies

  11. The CROSTVOC project - an integrated approach to study the effect of stress on BVOC exchange between agricultural crops and grassland ecosystems and the atmosphere

    Science.gov (United States)

    Amelynck, Crist; Heinesch, Bernard; Aubinet, Marc; Bachy, Aurélie; Delaplace, Pierre; Digrado, Anthony; du Jardin, Patrick; Fauconnier, Marie-Laure; Mozaffar, Ahsan; Schoon, Niels

    2015-04-01

    Global changes in atmospheric composition and climate are expected to affect BVOC exchange between terrestrial vegetation and the atmosphere through changes in the drivers of constitutive BVOC emissions and by increases in frequency and intensity of biotic or abiotic stress episodes. Indeed, several studies indicate changes in the emission patterns of constitutive BVOCs and emission of stress-induced BVOCs following heat, drought and oxidative stress, amongst others. Relating changes in BVOC emissions to the occurrence of one or multiple stressors in natural environmental conditions is not straightforward and only few field studies have dealt with it, especially for agricultural crop and grassland ecosystems. The CROSTVOC project aims to contribute in filling this knowledge gap in three ways. Firstly, it aims at performing long-term BVOC emission field measurements from maize (Zea mays L.) and wheat (Triticum aestivum L.), two important crop species on the global scale, and from grassland. This should lead to a better characterization of (mainly oxygenated) BVOC emissions from these understudied ecosystems, allowing a better representation of those emissions in air quality and atmospheric chemistry and transport models. BVOC fluxes are obtained by the Disjunct Eddy Covariance by mass scanning (DEC-MS) technique, using a hs-PTR-MS instrument for BVOC analysis. Secondly, the eddy covariance BVOC flux measurements (especially at the grassland site) will be accompanied by ozone flux, chlorophyll fluorescence, photosynthesis and soil moisture measurements, amongst others, to allow linking alterations in BVOC emissions to stress episodes. Simultaneously, automated dynamic enclosures will be deployed in order to detect specific abiotic and biotic stress markers by PTR-MS and identify them unambiguously by GC-MS. Thirdly, the field measurements will be accompanied by laboratory BVOC flux measurements in an environmental chamber in order to better disentangle the responses

  12. Characterisation of the semi-volatile component of Dissolved Organic Matter by Thermal Desorption - Proton Transfer Reaction - Mass Spectrometry

    NARCIS (Netherlands)

    Materić, Dušan; Peacock, Mike; Kent, Matthew; Cook, Sarah; Gauci, Vincent; Röckmann, Thomas; Holzinger, Rupert

    2017-01-01

    Proton Transfer Reaction - Mass Spectrometry (PTR-MS) is a sensitive, soft ionisation method suitable for qualitative and quantitative analysis of volatile and semi-volatile organic vapours. PTR-MS is used for various environmental applications including monitoring of volatile organic compounds

  13. Covering the different steps of the coffee processing: Can headspace VOC emissions be exploited to successfully distinguish between Arabica and Robusta?

    Science.gov (United States)

    Colzi, Ilaria; Taiti, Cosimo; Marone, Elettra; Magnelli, Susanna; Gonnelli, Cristina; Mancuso, Stefano

    2017-12-15

    This work was performed to evaluate the possible application of PTR-ToF-MS technique in distinguishing between Coffea arabica (Arabica) and Coffea canephora var. robusta (Robusta) commercial stocks in each step of the processing chain (green beans, roasted beans, ground coffee, brews). volatile organic compounds (VOC) spectra from coffee samples of 7 Arabica and 6 Robusta commercial stocks were recorded and submitted to multivariate statistical analysis. Results clearly showed that, in each stage of the coffee processing, the volatile composition of coffee is highly influenced by the species. Actually, with the exception of green beans, PTR-ToF-MS technique was able to correctly recognize Arabica and Robusta samples. Particularly, among 134 tentatively identified VOCs, some masses (16 for roasted coffee, 12 for ground coffee and 12 for brewed coffee) were found to significantly discriminate the two species. Therefore, headspace VOC analyses was showed to represent a valuable tool to distinguish between Arabica and Robusta. Copyright © 2017 Elsevier Ltd. All rights reserved.

  14. The impact of energy production on the atmosphere: Laboratory and field studies of emissions from oil and gas production and their chemical transformation

    Science.gov (United States)

    Li, Rui

    Over the past decades, the rapid development of energy production in the U.S. has led to significant changes in atmospheric emissions and transformation of trace gas and particles, which are still very uncertain and poorly understood. Through laboratory, modeling and field experiments we hope to better understand the trace gas emission and their contribution to secondary organic aerosols (SOA) formation in the oil and natural gas (O&NG) operations. A fast time-response Oxidation Flow Reactor (OFR) is used for the study of SOA formation from oil vapors. The radical chemistry and quantification of OH exposure (OHexp) in the reactor under various conditions were investigated using a photochemical kinetic model. An OHexp estimation equation derived from the model was shown to agree with measurements in several field campaigns. This work further establishes the usefulness of such reactors in atmospheric studies. Motivated from the SOA observations of Gulf of Mexico oil spill, the SOA formation from organic compounds of different volatility in the oil vapors was studied in the laboratory using OFR. We use the evaporation time dependence on volatility of the precursors to quantify their contribution to total SOA formation. This study shows (1) organic compounds of intermediate volatility contribute the large majority of SOA mass formed, (2) the mass spectral signature of SOA shows good agreement with that of ambient SOA formed during oil spill. These results in O&NG operations, the air toxic hydrogen sulfide (H 2S) can be released at wellheads, separation and storage tanks. Here, quantitative, fast time-response measurements of H2S using Proton-Transfer-Reaction Mass-Spectrometry (PTR-MS) instruments in an O&NG field are presented. A laboratory calibration study was performed to measure the humidity dependent sensitivities of H2S. The close correlation between H2S and CH4 and significant H2S levels downwind of storage tanks suggest that H2S emissions associated with O

  15. Synthetic nebular emission from massive galaxies - I: origin of the cosmic evolution of optical emission-line ratios

    Science.gov (United States)

    Hirschmann, Michaela; Charlot, Stephane; Feltre, Anna; Naab, Thorsten; Choi, Ena; Ostriker, Jeremiah P.; Somerville, Rachel S.

    2017-12-01

    Galaxies occupy different regions of the [O III]λ5007/H β-versus-[N II]λ6584/H α emission-line ratio diagram in the distant and local Universe. We investigate the origin of this intriguing result by modelling self-consistently, for the first time, nebular emission from young stars, accreting black holes (BHs) and older, post-asymptotic giant branch (post-AGB) stellar populations in galaxy formation simulations in a full cosmological context. In post-processing, we couple new-generation nebular-emission models with high-resolution, cosmological zoom-in simulations of massive galaxies to explore which galaxy physical properties drive the redshift evolution of the optical-line ratios [O III]λ5007/H β, [N II]λ6584/H α, [S II]λλ6717, 6731/H α and [O I]λ6300/H α. The line ratios of simulated galaxies agree well with observations of both star-forming and active local Sloan Digital Sky Survey galaxies. Towards higher redshifts, at fixed galaxy stellar mass, the average [O III]/H β is predicted to increase and [N II]/H α, [S II]/H α and [O I]/H α to decrease - widely consistent with observations. At fixed stellar mass, we identify star formation history, which controls nebular emission from young stars via the ionization parameter, as the primary driver of the cosmic evolution of [O III]/H β and [N II]/H α. For [S II]/H α and [O I]/H α, this applies only to redshifts greater than z = 1.5, the evolution at lower redshift being driven in roughly equal parts by nebular emission from active galactic nuclei and post-AGB stellar populations. Instead, changes in the hardness of ionizing radiation, ionized-gas density, the prevalence of BH accretion relative to star formation and the dust-to-metal mass ratio (whose impact on the gas-phase N/O ratio we model at fixed O/H) play at most a minor role in the cosmic evolution of simulated galaxy line ratios.

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

    Science.gov (United States)

    Müller, M.; Graus, M.; Wisthaler, A.; Hansel, A.; Metzger, A.; Dommen, J.; Baltensperger, U.

    2012-01-01

    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 CmHnNoOp 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 solid #000; color: #000;">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 solid #000; color: #000;">OSCSOA were in the range of -0.34 to -0.31, in agreement with expected average carbon oxidation states of fresh SOA (solid #000; color: #000;">OSC = -0.5-0).

  17. Comparison of VOC measurements in Nashville, TN, during the southern oxidants study (SOS) 1999

    International Nuclear Information System (INIS)

    Grabmer, W.; Wisthaler, A.; Hansel, A.; Stroud, C.; Roberts, J.M.; Fehsenfeld, F.C.

    2002-01-01

    Full text: During the Southern Oxidants Study (SOS) 1999 Nashville campaign ambient air samples were analyzed at Cornelia Fort Airport (CFA) for organic compounds by two independent methods: 1) a gas chromatographic systems operated by NOAAs Aeronomy Laboratory, which performed immediate analysis of collected samples and 2) an in situ proton transfer reaction mass spectrometer (PTR-MS) system operated by the Univ. of Innsbruck. The sample protocols were quite different for the different methods. The GC system sequentially collected and analyzed air samples each 60 minutes for VOCs. The in-situ PTR-MS system measured more than 20 VOCs on a time shared basis for 5 to 15 seconds respectively, once each 5 minutes. The PTR-MS system is not able to distinguish between isobaric species, therefore acetone and propanal (MVK and MACR) values measured by NOAAs GC were added up prior to comparison with the respective PTR-MS values. For all species mentioned above the different measurement methods show good agreement. (author)

  18. USE OF GC-MS/COMBUSTION/IRMS TO IDENTIFY AND DETERMINE THE STABLE CARBON ISOTOPIC RATIO OF INDIVIDUAL LIPIDS

    Science.gov (United States)

    A system that couples a gas chromatograph (GC) via a split to a quadrapole mass spectrometer (MS) and, through a combustion interface, to an isotope ratio mass spectrometer (IRMS) allows the simultaneous detection of electron impact mass spectra and stable carbon isotope ratio an...

  19. Refueling emissions from cars in Japan: Compositions, temperature dependence and effect of vapor liquefied collection system

    Science.gov (United States)

    Yamada, Hiroyuki; Inomata, Satoshi; Tanimoto, Hiroshi

    2015-11-01

    Refueling emissions from cars available on the Japanese market, which were not equipped with specific controlling devices, were investigated. For the composition analysis, a proton transfer reaction plus switchable reagent ion mass spectrometry (PTR + SRI-MS), which is capable of real-time measurement, was used. In addition, the performance of a vapor liquefied collection system (VLCS), which is a recently developed controlling device, was evaluated and compared with an onboard refueling vapor recovery (ORVR) system. The refueling emission factor of uncontrolled vehicles at 20 °C was 1.02 ± 0.40 g/L in the case dispensing 20 L of fuel. The results of composition analysis indicated that the maximum incremental reactivity (MIR) of refueling emissions in Japan was 3.49 ± 0.83. The emissions consist of 80% alkanes and 20% alkenes, and aromatics and di-enes were negligible. C4 alkene had the highest impact on the MIR of refueling emissions. The amounts of refueling emissions were well reproduced by a function developed by MOVE2010 in the temperature range of 5-35 °C. The compositions of the refueling emissions varied in this temperature range, but the change in MIR was negligible. The trapping efficiency of VLCS was the same level as that of the ORVR (over 95%). The MIRs of refueling and evaporative emissions were strongly affected by that of the test fuel. This study and our previous study indicated that MIRbreakthrough ≈ MIRrefueling ≈ MIRfuel + 0.5 and MIRpermeation ≈ MIRfuel. The real-world estimated average MIRfuel in Japan was about 3.0.

  20. Contribution of biogenic and photochemical sources to ambient VOCs during winter to summer transition at a semi-arid urban site in India.

    Science.gov (United States)

    Sahu, L K; Tripathi, Nidhi; Yadav, Ravi

    2017-10-01

    This paper presents the sources and characteristics of ambient volatile organic compounds (VOCs) measured using PTR-TOF-MS instrument in a metropolitan city of India during winter to summer transition period. Mixing ratios of VOCs exhibited strong diurnal, day-to-day and episodic variations. Methanol was the most dominant species with monthly mean values of 18-22 pbbv. The emission ratios of VOCs relative to benzene calculated from nighttime data were used to estimate the relative contributions of vehicle exhaust and other sources. The increasing daytime ratios of oxygenated-VOCs (OVOCs)/benzene and isoprene/benzene from February to March indicates increasing contribution of photo-oxidation and biogenic sources. Daytime fractions of acetone (18%), acetaldehyde (15%) and isoprene (4.5%) to the sum of measured VOCs in March were higher than those in February. Variations of VOCs at lower temperatures (biogenic emissions. The emissions of OVOCs from vehicle exhaust were estimated to be smaller (20-40%) than those from other sources. The contributions of biogenic and secondary sources to OVOCs and isoprene increased by 10-15% from winter to summer. This study provides evidence that the winter-to-summer transition has an impact on sources and composition of VOCs in tropical urban areas. Copyright © 2017 Elsevier Ltd. All rights reserved.

  1. Fast sorption measurements of volatile organic compounds on building materials: Part 1 – Methodology developed for field applications

    Directory of Open Access Journals (Sweden)

    M. Rizk

    2016-03-01

    Full Text Available A Proton Transfer Reaction-Mass Spectrometer (PTR-MS has been coupled to the outlet of a Field and Laboratory Emission Cell (FLEC, to measure volatile organic compounds (VOC concentration during a sorption experiments (Rizk et al., this issue [1]. The limits of detection of the PTR-MS for three VOCs are presented for different time resolution (2, 10 and 20 s. The mass transfer coefficient was calculated in the FLEC cavity for the different flow rates. The concentration profile obtained from a sorption experiment performed on a gypsum board and a vinyl flooring are also presented in comparison with the profile obtained for a Pyrex glass used as a material that do not present any sorption behavior (no sink. Finally, the correlation between the concentration of VOCs adsorbed on the surface of the gypsum board at equilibrium (Cse and the concentration of VOCs Ce measured in the gas phase at equilibrium is presented for benzene, C8 aromatics and toluene.

  2. Comparison of wintertime CO to NOx ratios to MOVES and MOBILE6.2 on-road emissions inventories

    Science.gov (United States)

    Wallace, H. W.; Jobson, B. T.; Erickson, M. H.; McCoskey, J. K.; VanReken, T. M.; Lamb, B. K.; Vaughan, J. K.; Hardy, R. J.; Cole, J. L.; Strachan, S. M.; Zhang, W.

    2012-12-01

    The CO-to-NOx molar emission ratios from the US EPA vehicle emissions models MOVES and MOBILE6.2 were compared to urban wintertime measurements of CO and NOx. Measurements of CO, NOx, and volatile organic compounds were made at a regional air monitoring site in Boise, Idaho for 2 months from December 2008 to January 2009. The site is impacted by roadway emissions from a nearby busy urban arterial roads and highway. The measured CO-to-NOx ratio for morning rush hour periods was 4.2 ± 0.6. The average CO-to-NOx ratio during weekdays between the hours of 08:00 and 18:00 when vehicle miles travelled were highest was 5.2 ± 0.5. For this time period, MOVES yields an average hourly CO-to-NOx ratio of 9.1 compared to 20.2 for MOBILE6.2. Off-network emissions are a significant fraction of the CO and NOx emissions in MOVES, accounting for 65% of total CO emissions, and significantly increase the CO-to-NOx molar ratio. Observed ratios were more similar to the average hourly running emissions for urban roads determined by MOVES to be 4.3.

  3. Gas chromatography of organic microcontaminants using atomic emission and mass spectrometric detection combined in one instrument (GC-AED/MS)

    NARCIS (Netherlands)

    Mol, H.G.J.; Hankemeier, T.; Brinkman, U.A.T.

    1999-01-01

    This study describes the coupling of an atomic-emission detector and mass-spectrometric detector to a single gas chromatograph. Splitting of the column effluent enables simultaneous detection by atomic-emission detection (AED) and mass spectrometry (MS) and yields a powerful system for the target

  4. Volatile organic compounds in the western Mediterranean basin: urban and rural winter measurements during the DAURE campaign

    Directory of Open Access Journals (Sweden)

    R. Seco

    2013-04-01

    Full Text Available Atmospheric volatile organic compounds (VOCs have key environmental and biological roles, but little is known about the daily VOC mixing ratios in Mediterranean urban and natural environments. We measured VOC mixing ratios concurrently at an urban and a rural site during the winter DAURE campaign in the northeastern Iberian Peninsula, by means of PTR-MS at both locations: a PTR-Quad-MS at the urban site and a PTR-ToF-MS at the rural site. All VOC mixing ratios measured were higher at the urban site (e.g. acetaldehyde, isoprene, benzene, and toluene with averages up to 1.68, 0.31, 0.58 and 2.71 ppbv, respectively, with the exception of some short-chain oxygenated VOCs such as acetone (with similar averages of 0.7–1.6 ppbv at both sites. The average diurnal pattern also differed between the sites. Most of the VOCs at the urban location showed their highest mixing ratios in the morning and evening. These peaks coincided with traffic during rush hour, the main origin of most of the VOCs analyzed. Between these two peaks, the sea breeze transported the urban air inland, thus helping to lower the VOC loading at the urban site. At the rural site, most of the measured VOCs were advected by the midday sea breeze, yielding the highest daily VOC mixing ratios (e.g. acetaldehyde, isoprene, benzene, and toluene with averages up to 0.65, 0.07, 0.19, and 0.41 ppbv, respectively. Only biogenic monoterpenes showed a clear local origin at this site. In addition, the concentrations of fine particulate matter observed at both sites, together with the synoptic meteorological conditions and radio-sounding data, allowed the identification of different atmospheric scenarios that had a clear influence on the measured VOC mixing ratios. These results highlight the differences and relationships in VOC mixing ratios between nearby urban and rural areas in Mediterranean regions. Further research in other urban-rural areas is warranted to better understand the urban

  5. Detection of formaldehyde emissions from an industrial zone in the Yangtze River Delta region of China using a proton transfer reaction ion-drift chemical ionization mass spectrometer

    Science.gov (United States)

    Ma, Yan; Diao, Yiwei; Zhang, Bingjie; Wang, Weiwei; Ren, Xinrong; Yang, Dongsen; Wang, Ming; Shi, Xiaowen; Zheng, Jun

    2016-12-01

    A proton transfer reaction ion-drift chemical ionization mass spectrometer (PTR-ID-CIMS) equipped with a hydronium (H3+O) ion source was developed and deployed near an industrial zone in the Yangtze River Delta (YRD) region of China in spring 2015 to investigate industry-related emissions of volatile organic compounds (VOCs). Air pollutants including formaldehyde (HCHO), aromatics, and other trace gases (O3 and CO) were simultaneously measured. Humidity effects on the sensitivity of the PTR-ID-CIMS for HCHO detection were investigated and quantified. The performances of the PTR-ID-CIMS were also validated by intercomparing with offline HCHO measurement technique using 2,4-dinitrophenylhydrazone (DNPH) cartridges and the results showed fairly good agreement (slope = 0.81, R2 = 0.80). The PTR-ID-CIMS detection limit of HCHO (10 s, three-duty-cycle averages) was determined to be 0.9-2.4 (RH = 1-81.5 %) parts per billion by volume (ppbv) based on 3 times the standard deviations of the background signals. During the field study, observed HCHO concentrations ranged between 1.8 and 12.8 ppbv with a campaign average of 4.1 ± 1.6 ppbv, which was comparable with previous HCHO observations in other similar locations of China. However, HCHO diurnal profiles showed few features of secondary formation. In addition, time series of both HCHO and aromatic VOCs indicated strong influence from local emissions. Using a multiple linear regression fit model, on average the observed HCHO can be attributed to secondary formation (13.8 %), background level (27.0 %), and industry-related emissions, i.e., combustion sources (43.2 %) and chemical productions (16.0 %). Moreover, within the plumes the industry-related emissions can account for up to 69.2 % of the observed HCHO. This work has provided direct evidence of strong primary emissions of HCHO from industry-related activities. These primary HCHO sources can potentially have a strong impact on local and regional air pollution formation

  6. Aroma analysis and quality control of food using highly sensitive analytical methods

    International Nuclear Information System (INIS)

    Mayr, D.

    2003-02-01

    This thesis deals with the development of quality control methods for food based on headspace measurements by Proton-Transfer-Reaction Mass-Spectrometry (PTR-MS) and with aroma analysis of food using PTR-MS and Gas Chromatography-Olfactometry (GC-O). An objective method was developed for the determination of a herb extract's quality; this quality was checked by a sensory analysis until now. The concentrations of the volatile organic compounds (VOCs) in the headspace of 81 different batches were measured by PTR-MS. Based on the sensory judgment of the customer, characteristic differences in the emissions of 'good' and 'bad' quality samples were identified and a method for the quality control of this herb extract was developed. This novel method enables the producing company to check and ensure that they are only selling high-quality products and therefore avoid complaints of the customer. Furthermore this method can be used for controlling, optimizing and automating the production process. VOCs emitted by meat were investigated using PTR-MS to develop a rapid, non-destructive and quantitative technique for determination of the microbial contamination of meat. Meat samples (beef, pork and poultry) that were wrapped into different kinds of packages (air and vacuum) were stored in at 4 o C for up to 13 days. The emitted VOCs were measured as a function of storage time and identified partly. The concentration of many of the measured VOCs, e.g. sulfur compounds like methanethiol, dimethylsulfide and dimethyldisulfide, largely increased over the storage time. There were big differences in the emissions of normal air- and vacuum-packed meat. VOCs typically emitted by air-packaged meat were methanethiol, dimethylsulfide and dimethyldisulfide, while ethanol and methanol were found in vacuum-packaged meat. A comparison of the PTR-MS results with those obtained by a bacteriological examination performed at the same time showed strong correlations (up to 99 %) between the

  7. Luminosity dependence in the ratio of X-ray to infrared emission of QSOs

    International Nuclear Information System (INIS)

    Worrall, D.M.

    1987-01-01

    The correlation of X-ray and near-infrared luminosity is studied for a sample of radio-quiet QSOs. The X-ray to infrared ratio is found to decrease as the infrared luminosity increases. No preference is found between the correlations of X-ray luminosity with optical or infrared luminosity. This implies that optical and infrared emission are equally good predictors of X-ray emission. Source models which directly link infrared and X-ray emission are discussed, and a preference is found for a specific synchrotron self-Compton model. This model predicts the correct luminosity dependence of the X-ray to infrared ratio if certain conditions apply. 55 references

  8. Comparison of emission inventory and ambient concentration ratios of CO, NMOG, and NOx in California South Coast Air Basin

    International Nuclear Information System (INIS)

    Fujita, E.M.; Croes, B.E.; Bennett, C.L.; Lawson, D.R.; Lurmann, F.W.; Main, H.H.

    1992-01-01

    In the present study, the author performed a top-down validation of the reactive organic gas and carbon monoxide emission inventories for California's South Coast Air Basin by comparing speciation profiles for nonmethane organic gases (NMOG) and ratios of CO/NO x and NMOG/NO x derived from early-morning (0700 to 0800) ambient measurements taken during the 1987 Southern California Air Quality Study with the corresponding ratios and speciation profiles derived from day-specific, hourly, gridded emission inventories. Twenty separate comparisons were considered for each ratio, each representing a different combination of season, emission category, and spatial and temporal averaging of emissions. It was determined that the most appropriate comparison in summer was ambient pollutant ratios with ratios derived from morning on-road motrovehicle emission inventories, and in the fall, ambient ratios with ratios derived from overnight on-road motor vehicle emission inventories with some contribution from overnight stationary-source NO x emission inventories. From these comparisons, the ambient CO/CO x and NMOG/NO x ratios are about 1.5 and 2 to 2.5 times higher, respectively, than the corresponding inventory ratios. On the assumption that inventories of NO x emissions are reasonably correct, these results indicate that on-road motor vehicle CO and NMOG emissions are significantly underestimated. Comparisons of measured CO, NMOG, and NO x concentrations and CO/NO x and NMOG/NO x ratios with air quality model predictions obtained by the California Air Resources Board show similar differences

  9. Strontium isotope ratios - a possible tool to study the authenticity of Indian tea using MC-ICP-MS

    International Nuclear Information System (INIS)

    Lagad, Rupali A.; Alamelu, D.; Aggarwal, Suresh K.; Singh, Sunil K.

    2011-01-01

    In the present study, an analytical procedure based on determination of the Sr isotope ratio 87 Sr/ 86 Sr in the Indian tea samples by MC-ICP-MS was developed and applied to 28 tea samples from four different Indian regions. The 87 Sr/ 86 Sr isotope ratio of the tea samples in different Indian regions is strongly dependent on the soil and growth environment condition. The analysis results of 28 Indian tea samples revealed that 87 Sr/ 86 Sr atom ratio follows the order Darjeeling > Kangra > Assam > Munnar

  10. Comparison of VOC measurements in Nashville, TE, during the southern oxidants study (SOS) 1999

    International Nuclear Information System (INIS)

    Grabmer, W.; Wisthaler, A.; Hansel, A.; Stroud, C.; Roberts, J.M.; Fehsenfeld, F.C.

    2002-01-01

    During the Southern Oxidants Study (SOS) 1999 Nashville campaign ambient air samples were analyzed at Cornelia Fort Airport (CFA) for organic compounds by two independent methods: 1) a gas chromatographic systems operated by NOAAs Aeronomy Laboratory, which performed immediate analysis of collected samples and 2) an in situ proton transfer reaction mass spectrometer (PTR M S) system operated by the University of Innsbruck. The sample protocols were quite different for the different methods. The GC system sequentially collected and analyzed air samples each 60 minutes for VOCs. The in-situ PTR-MS system measured more than 20 VOCs on a time shared basis for 5 to 15 seconds respectively, once each five minutes. The PTR-MS system is not able to distinguish between isobaric species, therefor acetone and propanal (MVK and MACR) values measured by NOAAs GC were added up prior to comparison with the respective PTR-MS values. For all species mentioned above the different measurement methods show good agreement. (author)

  11. In cleanroom, sub-ppb real-time monitoring of volatile organic compounds using proton-transfer reaction/time of flight/mass spectrometry

    Science.gov (United States)

    Hayeck, Nathalie; Maillot, Philippe; Vitrani, Thomas; Pic, Nicolas; Wortham, Henri; Gligorovski, Sasho; Temime-Roussel, Brice; Mizzi, Aurélie; Poulet, Irène

    2014-04-01

    Refractory compounds such as Trimethylsilanol (TMS) and other organic compounds such as propylene glycol methyl ether acetate (PGMEA) used in the photolithography area of microelectronic cleanrooms have irreversible dramatic impact on optical lenses used on photolithography tools. There is a need for real-time, continuous measurements of organic contaminants in representative cleanroom environment especially in lithography zone. Such information is essential to properly evaluate the impact of organic contamination on optical lenses. In this study, a Proton-Transfer Reaction-Time-of-Flight Mass spectrometer (PTR-TOF-MS) was applied for real-time and continuous monitoring of fugitive organic contamination induced by the fabrication process. Three types of measurements were carried out using the PTR-TOF-MS in order to detect the volatile organic compounds (VOCs) next to the tools in the photolithography area and at the upstream and downstream of chemical filters used to purge the air in the cleanroom environment. A validation and verification of the results obtained with PTR-TOF-MS was performed by comparing these results with those obtained with an off-line technique that is Automated Thermal Desorber - Gas Chromatography - Mass Spectrometry (ATD-GC-MS) used as a reference analytical method. The emerged results from the PTR-TOF-MS analysis exhibited the temporal variation of the VOCs levels in the cleanroom environment during the fabrication process. While comparing the results emerging from the two techniques, a good agreement was found between the results obtained with PTR-TOF-MS and those obtained with ATD-GC-MS for the PGMEA, toluene and xylene. Regarding TMS, a significant difference was observed ascribed to the technical performance of both instruments.

  12. Forecasting the Allocation Ratio of Carbon Emission Allowance Currency for 2020 and 2030 in China

    Directory of Open Access Journals (Sweden)

    Shihong Zeng

    2016-07-01

    Full Text Available Many countries and scholars have used various strategies to improve and optimize the allocation ratios for carbon emission allowances. This issue is more urgent for China due to the uneven development across the country. This paper proposes a new method that divides low-carbon economy development processes into two separate periods: from 2020 to 2029 and from 2030 to 2050. These two periods have unique requirements and emissions reduction potential; therefore, they must involve different allocation methods, so that reduction behaviors do not stall the development of regional low-carbon economies. During the first period, a more deterministic economic development approach for the carbon emission allowance allocation ratio should be used. During the second period, more adaptive and optimized policy guidance should be employed. We developed a low-carbon economy index evaluation system using the entropy weight method to measure information filtering levels. We conducted vector autoregressive correlation tests, consulted 60 experts for the fuzzy analytic hierarchy process, and we conducted max-min standardized data processing tests. This article presents first- and second-period carbon emission allowance models in combination with a low-carbon economy index evaluation system. Finally, we forecast reasonable carbon emission allowance allocation ratios for China for the periods starting in 2020 and 2030. A good allocation ratio for the carbon emission allowance can help boost China’s economic development and help the country reach its energy conservation and emissions reduction goals.

  13. Virtual disjunct eddy covariance measurements of organic compound fluxes from a subalpine forest using proton transfer reaction mass spectrometry

    Directory of Open Access Journals (Sweden)

    T. G. Karl

    2002-01-01

    Full Text Available A `virtual' disjunct eddy covariance (vDEC device was tested with field measurements of biogenic VOC fluxes at a subalpine forest site in the Rocky Mountains of the USA. A PTR-MS instrument was used as the VOC sensor. Daily peak emission fluxes of 2-methyl-3-buten-2-ol (MBO, methanol, acetone and acetaldehyde were around 1.5, 1, 0.8 and 0.4 mg m-2 h-1, respectively. High pass filtering due to long sampling lines was investigated in laboratory experiments, and suggested that VOC losses in PTFA lines are generally governed by diffusion laws. Memory effects and surface reactions did not seem to play a dominant role. Model estimates of MBO fluxes compared well with measured fluxes. The results also suggest that latent heat and sensible heat fluxes are reasonably well correlated with VOC fluxes and could be used to predict variations in VOC emissions. The release of MBO, methanol, acetone and acetaldehyde resulted in significant change of tropospheric oxidant levels and a 10--40% increase in ozone levels, as inferred from a photochemical box model. We conclude that vDEC with a PTR-MS instrument is a versatile tool for simultaneous field analysis of multiple VOC fluxes.

  14. The performance of single and multi-collector ICP-MS instruments for fast and reliable 34S/32S isotope ratio measurements†

    Science.gov (United States)

    Pröfrock, Daniel; Irrgeher, Johanna; Prohaska, Thomas

    2016-01-01

    The performance and validation characteristics of different single collector inductively coupled plasma mass spectrometers based on different technical principles (ICP-SFMS, ICP-QMS in reaction and collision modes, and ICP-MS/MS) were evaluated in comparison to the performance of MC ICP-MS for fast and reliable S isotope ratio measurements. The validation included the determination of LOD, BEC, measurement repeatability, within-lab reproducibility and deviation from certified values as well as a study on instrumental isotopic fractionation (IIF) and the calculation of the combined standard measurement uncertainty. Different approaches of correction for IIF applying external intra-elemental IIF correction (aka standard-sample bracketing) using certified S reference materials and internal inter-elemental IIF (aka internal standardization) correction using Si isotope ratios in MC ICP-MS are explained and compared. The resulting combined standard uncertainties of examined ICP-QMS systems were not better than 0.3–0.5% (uc,rel), which is in general insufficient to differentiate natural S isotope variations. Although the performance of the single collector ICP-SFMS is better (single measurement uc,rel = 0.08%), the measurement reproducibility (>0.2%) is the major limit of this system and leaves room for improvement. MC ICP-MS operated in the edge mass resolution mode, applying bracketing for correction of IIF, provided isotope ratio values with the highest quality (relative combined measurement uncertainty: 0.02%; deviation from the certified value: <0.002%). PMID:27812369

  15. Green leaf volatiles and oxygenated metabolite emission bursts from mesquite branches following light-dark transitions.

    Science.gov (United States)

    Jardine, K; Barron-Gafford, G A; Norman, J P; Abrell, L; Monson, R K; Meyers, K T; Pavao-Zuckerman, M; Dontsova, K; Kleist, E; Werner, C; Huxman, T E

    2012-09-01

    Green leaf volatiles (GLVs) are a diverse group of fatty acid-derived compounds emitted by all plants and are involved in a wide variety of developmental and stress-related biological functions. Recently, GLV emission bursts from leaves were reported following light-dark transitions and hypothesized to be related to the stress response while acetaldehyde bursts were hypothesized to be due to the 'pyruvate overflow' mechanism. In this study, branch emissions of GLVs and a group of oxygenated metabolites (acetaldehyde, ethanol, acetic acid, and acetone) derived from the pyruvate dehydrogenase (PDH) bypass pathway were quantified from mesquite plants following light-dark transitions using a coupled GC-MS, PTR-MS, and photosynthesis system. Within the first minute after darkening following a light period, large emission bursts of both C(5) and C(6) GLVs dominated by (Z)-3-hexen-1-yl acetate together with the PDH bypass metabolites are reported for the first time. We found that branches exposed to CO(2)-free air lacked significant GLV and PDH bypass bursts while O(2)-free atmospheres eliminated the GLV burst but stimulated the PDH bypass burst. A positive relationship was observed between photosynthetic activity prior to darkening and the magnitude of the GLV and PDH bursts. Photosynthesis under (13)CO(2) resulted in bursts with extensive labeling of acetaldehyde, ethanol, and the acetate but not the C(6)-alcohol moiety of (Z)-3-hexen-1-yl acetate. Our observations are consistent with (1) the "pyruvate overflow" mechanism with a fast turnover time (3 h) responsible for the C(6) alcohol moiety of (Z)-3-hexen-1-yl acetate via the 13-lipoxygenase pathway. We conclude that our non-invasive method may provide a new valuable in vivo tool for studies of acetyl-CoA and fatty acid metabolism in plants at a variety of spatial scales.

  16. A study on the variation of strontium isotopic ratio in Darjeeling tea using MC-ICP-MS

    International Nuclear Information System (INIS)

    Lagad, Rupali A.; Alamelu, D.; Jagadish Kumar, S.; Aggarwal, Suresh K.; Rai, Vinai; Singh, S.K.

    2011-01-01

    In the present study, an analytical procedure based on the determination of the Sr isotope ratio 87 Sr/ 86 Sr in the Darjeeling tea samples by MC-ICP-MS was developed and applied to 15 green tea samples obtained from different tea gardens in Darjeeling. Variation in 87 Sr/ 86 Sr ratio was observed among eleven different tea gardens fro different geographical locations. The obtained data on 87 Sr/ 86 Sr ration in authentic tea leaves samples can be useful while comparing it with processed tea samples from respective regions

  17. Coupling field and laboratory measurements to estimate the emission factors of identified and unidentified trace gases for prescribed fires

    Directory of Open Access Journals (Sweden)

    R. J. Yokelson

    2013-01-01

    Full Text Available An extensive program of experiments focused on biomass burning emissions began with a laboratory phase in which vegetative fuels commonly consumed in prescribed fires were collected in the southeastern and southwestern US and burned in a series of 71 fires at the US Forest Service Fire Sciences Laboratory in Missoula, Montana. The particulate matter (PM2.5 emissions were measured by gravimetric filter sampling with subsequent analysis for elemental carbon (EC, organic carbon (OC, and 38 elements. The trace gas emissions were measured by an open-path Fourier transform infrared (OP-FTIR spectrometer, proton-transfer-reaction mass spectrometry (PTR-MS, proton-transfer ion-trap mass spectrometry (PIT-MS, negative-ion proton-transfer chemical-ionization mass spectrometry (NI-PT-CIMS, and gas chromatography with MS detection (GC-MS. 204 trace gas species (mostly non-methane organic compounds (NMOC were identified and quantified with the above instruments. Many of the 182 species quantified by the GC-MS have rarely, if ever, been measured in smoke before. An additional 153 significant peaks in the unit mass resolution mass spectra were quantified, but either could not be identified or most of the signal at that molecular mass was unaccounted for by identifiable species.

    In a second, "field" phase of this program, airborne and ground-based measurements were made of the emissions from prescribed fires that were mostly located in the same land management units where the fuels for the lab fires were collected. A broad variety, but smaller number of species (21 trace gas species and PM2.5 was measured on 14 fires in chaparral and oak savanna in the southwestern US, as well as pine forest understory in the southeastern US and Sierra Nevada mountains of California. The field measurements of emission factors (EF are useful both for modeling and to examine the representativeness of our lab fire EF. The lab EF/field EF ratio for

  18. Submicron particulate organic matter in the urban atmosphere: a new method for real-time measurement, molecular-level characterization and source apportionment

    Science.gov (United States)

    Müller, Markus; Eichler, Philipp; D'Anna, Barbara; Tan, Wen; Wisthaler, Armin

    2017-04-01

    We used a novel chemical analytical method for measuring submicron particulate organic matter in the atmosphere of three European cities (Innsbruck, Lyon, Valencia). Proton-Transfer-Reaction Time-of-Flight Mass Spectrometry (PTR-ToF-MS) was used in combination with the "chemical analysis of aerosol online" (CHARON) inlet for detecting particulate organic compounds on-line (i.e. without filter pre-collection), in real-time (1-min time resolution), at ng m-3 concentrations, with molecular-level resolution (i.e. obtaining molecular weight and elemental composition information). The CHARON-PTR-ToF-MS system monitored molecular tracers associated with different particle sources including levoglucosan from biomass combustion, PAHs from vehicular traffic, nicotine from cigarette smoking, and monoterpene oxidation products secondarily formed from biogenic emissions. The tracer information was used for interpreting positive matrix factorization (PMF) data which allowed us to apportion the sources of submicron particulate organic matter in the different urban environments. This work was funded through the PIMMS ITN, which was supported by the European Commission's 7th Framework Programme under grant agreement number 287382.

  19. Flux measurement of methanol, acetaldehyde and other oxygenated VOCs from crop harvesting using proton-transfer-reaction mass spectrometry and surface layer gradient method

    International Nuclear Information System (INIS)

    Lindinger, C.; Jordan, A.; Karl, T.; Guenther, A.; Tschiersch, J.; Ruckerbauer, F.; Paretzke, H.

    2002-01-01

    PTR-MS technique was used to measure fluxes of various VOC's including oxygenates using surface layer gradient method. The VOC concentrations and temperature were measured at heights of about 0.5 m and 3.9 m above ground at field site in St. Johann in Tirol during and after grass cutting (24th and 25th of May 2000) in order to calculate fluxes. The sensible heat flux was obtained by a sonic anemometer with turbulence data analyzer. The major crop in this part of Austria are perennial grasses used for livestock farming. We observed VOC emission fluxes including methanol and acetaldehyde as the major volatile, C 5 and C 6 leaf wound compounds with lesser amounts and traces of acetone and butanone. This composition of VOC's is very similar to that released from slashed pasture grass. At the same time, VOC fluxes were measured with PTR-MS and eddy covariance method. Comparing the flux data of methanol and acetaldehyde of both days have shown very similar results. (author)

  20. Investigations of chemical warfare agents and toxic industrial compounds with proton-transfer-reaction mass spectrometry for a real-time threat monitoring scenario.

    Science.gov (United States)

    Kassebacher, Thomas; Sulzer, Philipp; Jürschik, Simone; Hartungen, Eugen; Jordan, Alfons; Edtbauer, Achim; Feil, Stefan; Hanel, Gernot; Jaksch, Stefan; Märk, Lukas; Mayhew, Chris A; Märk, Tilmann D

    2013-01-30

    Security and protection against terrorist attacks are major issues in modern society. One especially challenging task is the monitoring and protection of air conditioning and heating systems of buildings against terrorist attacks with toxic chemicals. As existing technologies have low selectivity, long response times or insufficient sensitivity, there is a need for a novel approach such as we present here. We have analyzed various chemical warfare agents (CWAs) and/or toxic industrial compounds (TICs) and related compounds, namely phosgene, diphosgene, chloroacetone, chloroacetophenone, diisopropylaminoethanol, and triethyl phosphate, utilizing a high-resolution proton-transfer-reaction time-of-flight mass spectrometry (PTR-TOFMS) instrument with the objective of finding key product ions and their intensities, which will allow a low-resolution quadrupole mass spectrometry based PTR-MS system to be used with high confidence in the assignment of threat agents in the atmosphere. We obtained high accuracy PTR-TOFMS mass spectra of the six compounds under study at two different values for the reduced electric field in the drift tube (E/N). From these data we have compiled a table containing product ions, and isotopic and E/N ratios for highly selective threat compound detection with a compact and cost-effective quadrupole-based PTR-MS instrument. Furthermore, using chloroacetophenone (tear gas), we demonstrated that this instrument's response is highly linear in the concentration range of typical Acute Exposure Guideline Levels (AEGLs). On the basis of the presented results it is possible to develop a compact and cost-effective PTR-QMS instrument that monitors air supply systems and triggers an alarm as soon as the presence of a threat agent is detected. We hope that this real-time surveillance device will help to seriously improve safety and security in environments vulnerable to terrorist attacks with toxic chemicals. Copyright © 2012 John Wiley & Sons, Ltd.

  1. Eddy covariance flux measurements of biogenic VOCs during ECHO 2003 using proton transfer reaction mass spectrometry

    Directory of Open Access Journals (Sweden)

    C. Spirig

    2005-01-01

    Full Text Available Within the framework of the AFO 2000 project ECHO, two PTR-MS instruments were operated in combination with sonic anemometers to determine biogenic VOC fluxes from a mixed deciduous forest site in North-Western Germany. The measurement site was characterised by a forest of inhomogeneous composition, complex canopy structure, limited extension in certain wind directions and frequent calm wind conditions during night time. The eddy covariance (EC technique was applied since it represents the most direct flux measurement approach on the canopy scale and is, therefore, least susceptible to these non-ideal conditions. A specific flux calculation method was used to account for the sequential multi-component PTR-MS measurements and allowing an individual delay time adjustment as well as a rigorous quality control based on cospectral analysis. The validated flux results are consistent with light and temperature dependent emissions of isoprene and monoterpenes from this forest, with average daytime emissions of 0.94 and 0.3µg m-2s-1, respectively. Emissions of methanol reached on average 0.087µg m-2s-1 during daytime, but fluxes were too small to be detected during night time. Upward fluxes of the isoprene oxidation products methyl vinyl ketone (MVK and methacrolein (MACR were also found, being two orders of magnitude lower than those of isoprene. Calculations with an analytical footprint model indicate that the observed isoprene fluxes correlate with the fraction of oaks within the footprints of the flux measurement.

  2. Coupling field and laboratory measurements to estimate the emission factors of identified and unidentified trace gases for prescribed fires

    Energy Technology Data Exchange (ETDEWEB)

    Yokelson, R. J.; Burling, I. R.; Gilman, J. B.; Warneke, C.; Stockwell, C. E.; de Gouw, J.; Akagi, S. K.; Urbanski, S. P.; Veres, P.; Roberts, J. M.; Kuster, W. C.; Reardon, J.; Griffith, D. W. T.; Johnson, T. J.; Hosseini, S.; Miller, J. W.; Cocker III, D. R.; Jung, H.; Weise, D. R.

    2013-01-01

    Vegetative fuels commonly consumed in prescribed fires were collected from five locations in the southeastern and southwestern U.S. and burned in a series of 77 fires at the U.S. Forest Service Fire Sciences Laboratory in Missoula, Montana. The particulate matter (PM2.5) emissions were measured by gravimetric filter sampling with subsequent analysis for elemental carbon (EC), organic carbon (OC), and 38 elements. The trace gas emissions were measured with a large suite of state-of-the-art instrumentation including an open-path Fourier transform infrared (OP FTIR) spectrometer, proton-transfer-reaction mass spectrometry (PTR-MS), proton-transfer ion-trap mass spectrometry (PIT-MS), negative-ion proton-transfer chemical-ionization mass spectrometry (NI-PT-CIMS), and gas chromatography with MS detection (GC-MS). 204 trace gas species (mostly non-methane organic compounds (NMOC)) were identified and quantified with the above instruments. An additional 152 significant peaks in the unit mass resolution mass spectra were quantified, but either could not be identified or most of the signal at that molecular mass was unaccounted for by identifiable species. As phase II of this study, we conducted airborne and ground-based sampling of the emissions from real prescribed fires mostly in the same land management units where the fuels for the lab fires were collected. A broad variety, but smaller number of species (21 trace gas species and PM2.5) was measured on 14 fires in chaparral and oak savanna in the southwestern US, as well as pine forest understory in the southeastern US and Sierra Nevada mountains of California. These extensive field measurements of emission factors (EF) for temperate biomass burning are useful both for modeling and to examine the representativeness of our lab fire EF. The lab/field EF ratio for the pine understory fuels was not statistically different from one, on average. However, our lab EF for “smoldering compounds” emitted by burning the semi

  3. Recent Progress and Emerging Issues in Measuring and Modeling Biomass Burning Emissions

    Science.gov (United States)

    Yokelson, R. J.; Stockwell, C.; Veres, P. R.; Hatch, L. E.; Barsanti, K. C.; Simpson, I. J.; Blake, D. R.; Alvarado, M.; Kreidenweis, S. M.; Robinson, A. L.; Akagi, S. K.; McMeeking, G. R.; Stone, E.; Gilman, J.; Warneke, C.; Sedlacek, A. J.; Kleinman, L. I.

    2013-12-01

    Nine recent multi-PI campaigns (6 airborne, 3 laboratory) have quantified biomass burning emissions and the subsequent smoke evolution in unprecedented detail. Among these projects were the Fourth Fire Lab at Missoula Experiment (FLAME-4) and the DOE airborne campaign BBOP (Biomass Burning Observation Project). Between 2009 and 2013 a large selection of fuels and ecosystems were probed including: (1) 21 US prescribed fires in pine forests, chaparral, and shrublands; (2) numerous wildfires in the Pacific Northwest of the US; (3) 77 lab fires burning fuels collected from the sites of the prescribed fires; and (4) 158 lab fires burning authentic fuels in traditional cooking fires and advanced stoves; peat from Indonesia, Canada, and North Carolina; savanna grasses from Africa; temperate grasses from the US; crop waste from the US; rice straw from Taiwan, China, Malaysia, and California; temperate and boreal forest fuels collected in Montana and Alaska; chaparral fuels from California; trash; and tires. Instrumentation for gases included: FTIR, PTR-TOF-MS, 2D-GC and whole air sampling. Particle measurements included filter sampling (with IC, elemental carbon (EC), organic carbon (OC), and GC-MS) and numerous real-time measurements such as: HR-AMS (high-resolution aerosol MS), SP-AMS (soot particle AMS), SP2 (single particle soot photometer), SP-MS (single particle MS), ice nuclei, CCN (cloud condensation nuclei), water soluble OC, size distribution, and optical properties in the UV-VIS. New data include: emission factors for over 400 gases, black carbon (BC), brown carbon (BrC), organic aerosol (OA), ions, metals, EC, and OC; and details of particle morphology, mixing state, optical properties, size distributions, and cloud nucleating activity. Large concentrations (several ppm) of monoterpenes were present in fresh smoke. About 30-70% of the initially emitted gas-phase non-methane organic compounds were semivolatile and could not be identified with current technology

  4. Leaf level emissions of volatile organic compounds (VOC) from some Amazonian and Mediterranean plants

    Science.gov (United States)

    Bracho-Nunez, A.; Knothe, , N. M.; Welter, S.; Staudt, M.; Costa, W. R.; Liberato, M. A. R.; Piedade, M. T. F.; Kesselmeier, J.

    2013-09-01

    Emission inventories defining regional and global biogenic volatile organic compounds (VOC) emission strengths are needed to determine the impact of VOC on atmospheric chemistry (oxidative capacity) and physics (secondary organic aerosol formation and effects). The aim of this work was to contribute with measurements of tree species from the poorly described tropical vegetation in direct comparison with the quite well-investigated, highly heterogeneous emissions from Mediterranean vegetation. VOC emission from sixteen plant species from the Mediterranean area were compared with twelve plant species from different environments of the Amazon basin by an emission screening at leaf level using branch enclosures. Analysis of the volatile organics was performed online by a proton-transfer-reaction mass spectrometer (PTR-MS) and offline by collection on adsorbent tubes and subsequent gas chromatographic analysis. Isoprene was the most dominant compound emitted followed by monoterpenes, methanol and acetone. The average loss rates of VOC carbon in relation to the net CO2 assimilation were found below 4% and indicating normal unstressed plant behavior. Most of the Mediterranean species emitted a large variety of monoterpenes, whereas only five tropical species were identified as monoterpene emitters exhibiting a quite conservative emission pattern (α-pinene plants showed additional emissions of sesquiterpenes. In the case of Amazonian plants no sesquiterpenes were detected. However, missing of sesquiterpenes may also be due to a lack of sensitivity of the measuring systems. Furthermore, our screening activities cover only 1% of tree species of such tropical areas as estimated based on recent biodiversity reports. Methanol emissions, an indicator of growth, were found to be common in most of the tropical and Mediterranean species. A few species from both ecosystems showed acetone emissions. The observed heterogeneous emissions, including reactive VOC species which are not

  5. Leaf level emissions of volatile organic compounds (VOC from some Amazonian and Mediterranean plants

    Directory of Open Access Journals (Sweden)

    A. Bracho-Nunez

    2013-09-01

    Full Text Available Emission inventories defining regional and global biogenic volatile organic compounds (VOC emission strengths are needed to determine the impact of VOC on atmospheric chemistry (oxidative capacity and physics (secondary organic aerosol formation and effects. The aim of this work was to contribute with measurements of tree species from the poorly described tropical vegetation in direct comparison with the quite well-investigated, highly heterogeneous emissions from Mediterranean vegetation. VOC emission from sixteen plant species from the Mediterranean area were compared with twelve plant species from different environments of the Amazon basin by an emission screening at leaf level using branch enclosures. Analysis of the volatile organics was performed online by a proton-transfer-reaction mass spectrometer (PTR-MS and offline by collection on adsorbent tubes and subsequent gas chromatographic analysis. Isoprene was the most dominant compound emitted followed by monoterpenes, methanol and acetone. The average loss rates of VOC carbon in relation to the net CO2 assimilation were found below 4% and indicating normal unstressed plant behavior. Most of the Mediterranean species emitted a large variety of monoterpenes, whereas only five tropical species were identified as monoterpene emitters exhibiting a quite conservative emission pattern (α-pinene < limonene < sabinene < ß-pinene. Mediterranean plants showed additional emissions of sesquiterpenes. In the case of Amazonian plants no sesquiterpenes were detected. However, missing of sesquiterpenes may also be due to a lack of sensitivity of the measuring systems. Furthermore, our screening activities cover only 1% of tree species of such tropical areas as estimated based on recent biodiversity reports. Methanol emissions, an indicator of growth, were found to be common in most of the tropical and Mediterranean species. A few species from both ecosystems showed acetone emissions. The observed

  6. Exploring the relation between urbanization and residential CO2 emissions in China: a PTR approach

    OpenAIRE

    Hu, Zongyi; Tang, Liwei

    2013-01-01

    Recent empirical work suggests that urbanization and residential CO2 emissions are related. This paper investigates the nonlinear impact of urbanization on residential CO2 emissions over the period 1997–2011 in China by applying the Candelon et al. (2012) methodology. The results show that the relationship between urbanization and residential CO2 emissions is negative over the sample which is inconsistent with the previous studies. In addition, we find the absolute difference of the estimated...

  7. Simultaneous measurement of quantum yield ratio and absorption ratio between acceptor and donor by linearly unmixing excitation-emission spectra.

    Science.gov (United States)

    Zhang, C; Lin, F; DU, M; Qu, W; Mai, Z; Qu, J; Chen, T

    2018-02-13

    Quantum yield ratio (Q A /Q D ) and absorption ratio (K A /K D ) in all excitation wavelengths used between acceptor and donor are indispensable to quantitative fluorescence resonance energy transfer (FRET) measurement based on linearly unmixing excitation-emission spectra (ExEm-spFRET). We here describe an approach to simultaneously measure Q A /Q D and K A /K D values by linearly unmixing the excitation-emission spectra of at least two different donor-acceptor tandem constructs with unknown FRET efficiency. To measure the Q A /Q D and K A /K D values of Venus (V) to Cerulean (C), we used a wide-field fluorescence microscope to image living HepG2 cells separately expressing each of four different C-V tandem constructs at different emission wavelengths with 435 nm and 470 nm excitation respectively to obtain the corresponding excitation-emission spectrum (S DA ). Every S DA was linearly unmixed into the contributions (weights) of three excitation-emission spectra of donor (W D ) and acceptor (W A ) as well as donor-acceptor sensitisation (W S ). Plot of W S /W D versus W A /W D for the four C-V plasmids from at least 40 cells indicated a linear relationship with 1.865 of absolute intercept (Q A /Q D ) and 0.273 of the reciprocal of slope (K A /K D ), which was validated by quantitative FRET measurements adopting 1.865 of Q A /Q D and 0.273 of K A /K D for C32V, C5V, CVC and VCV constructs respectively in living HepG2 cells. © 2018 The Authors Journal of Microscopy © 2018 Royal Microscopical Society.

  8. A new method of organizing spectral line intensity ratio fluctuations of nightglow emissions

    International Nuclear Information System (INIS)

    Thelin, B.

    1986-02-01

    In this paper a new kind of linearization effect between the atmospheric night airglow emissions is presented. The same kind of linearization effect has previously been studied with spectrochemical light sources together with a spectrometer. A linear graph was obtained for atomic spectral lines and vibrational bandspectra when the spectral line intensity ratio fluctuations were plotted versus the photon energies of these emissions. To study this effect data from a number of different photometer investigations of night airglow emissions at different times and places have been used. (author)

  9. Analysis of plutonium isotope ratios including 238Pu/239Pu in individual U-Pu mixed oxide particles by means of a combination of alpha spectrometry and ICP-MS.

    Science.gov (United States)

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

    2017-04-01

    Isotope ratio analysis of individual uranium-plutonium (U-Pu) mixed oxide particles contained within environmental samples taken from nuclear facilities is proving to be increasingly important in the field of nuclear safeguards. However, isobaric interferences, such as 238 U with 238 Pu and 241 Am with 241 Pu, make it difficult to determine plutonium isotope ratios in mass spectrometric measurements. In the present study, the isotope ratios of 238 Pu/ 239 Pu, 240 Pu/ 239 Pu, 241 Pu/ 239 Pu, and 242 Pu/ 239 Pu were measured for individual Pu and U-Pu mixed oxide particles by a combination of alpha spectrometry and inductively coupled plasma mass spectrometry (ICP-MS). As a consequence, we were able to determine the 240 Pu/ 239 Pu, 241 Pu/ 239 Pu, and 242 Pu/ 239 Pu isotope ratios with ICP-MS after particle dissolution and chemical separation of plutonium with UTEVA resins. Furthermore, 238 Pu/ 239 Pu isotope ratios were able to be calculated by using both the 238 Pu/( 239 Pu+ 240 Pu) activity ratios that had been measured through alpha spectrometry and the 240 Pu/ 239 Pu isotope ratios determined through ICP-MS. Therefore, the combined use of alpha spectrometry and ICP-MS is useful in determining plutonium isotope ratios, including 238 Pu/ 239 Pu, in individual U-Pu mixed oxide particles. Copyright © 2016 Elsevier B.V. All rights reserved.

  10. Influence of Compression Ratio on the Performance and Emission Characteristics of Annona Methyl Ester Operated DI Diesel Engine

    Directory of Open Access Journals (Sweden)

    Senthil Ramalingam

    2014-09-01

    Full Text Available This study aims to find the optimum performance and emission characteristics of single cylinder variable compression ratio (VCR engine with different blends of Annona methyl ester (AME as fuel. The performance parameters such as specific fuel consumption (SFC, brake thermal efficiency (BTE, and emission levels of HC, CO, Smoke, and NOx were compared with the diesel fuel. It is found that, at compression ratio of 17: 1 for A20 blended fuel (20% AME + 80% Diesel shows better performance and lower emission level which is very close to neat diesel fuel. The engine was operated with different values of compression ratio (15, 16, and 17 to find out best possible combination for operating engine with blends of AME. It is also found that the increase of compression ratio increases the BTE and reduces SFC and has lower emission without any engine in design modifications.

  11. Chemistry of Volatile Organic Compounds in the Los Angeles basin: Nighttime Removal of Alkenes and Determination of Emission Ratios

    Science.gov (United States)

    de Gouw, J. A.; Gilman, J. B.; Kim, S.-W.; Lerner, B. M.; Isaacman-VanWertz, G.; McDonald, B. C.; Warneke, C.; Kuster, W. C.; Lefer, B. L.; Griffith, S. M.; Dusanter, S.; Stevens, P. S.; Stutz, J.

    2017-11-01

    We reanalyze a data set of hydrocarbons in ambient air obtained by gas chromatography-mass spectrometry at a surface site in Pasadena in the Los Angeles basin during the NOAA California Nexus study in 2010. The number of hydrocarbon compounds quantified from the chromatograms is expanded through the use of new peak-fitting data analysis software. We also reexamine hydrocarbon removal processes. For alkanes, small alkenes, and aromatics, the removal is determined by the reaction with hydroxyl (OH) radicals. For several highly reactive alkenes, the nighttime removal by ozone and nitrate (NO3) radicals is also significant. We discuss how this nighttime removal affects the determination of emission ratios versus carbon monoxide (CO) and show that previous estimates based on nighttime correlations with CO were too low. We analyze model output from the Weather Research and Forecasting-Chemistry model for hydrocarbons and radicals at the Pasadena location to evaluate our methods for determining emission ratios from the measurements. We find that our methods agree with the modeled emission ratios for the domain centered on Pasadena and that the modeled emission ratios vary by 23% across the wider South Coast basin. We compare the alkene emission ratios with published results from ambient measurements and from tunnel and dynamometer studies of motor vehicle emissions. We find that with few exceptions the composition of alkene emissions determined from the measurements in Pasadena closely resembles that of motor vehicle emissions.

  12. Development of routines for simultaneous in situ chemical composition and stable Si isotope ratio analysis by femtosecond laser ablation inductively coupled plasma mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Frick, Daniel A., E-mail: dfrick@gfz-potsdam.de [GFZ German Research Centre for Geosciences, 14473 Potsdam (Germany); Schuessler, Jan A. [GFZ German Research Centre for Geosciences, 14473 Potsdam (Germany); Blanckenburg, Friedhelm von [GFZ German Research Centre for Geosciences, 14473 Potsdam (Germany); Institute of Geological Science, Freie Universität Berlin, 12249 Berlin (Germany)

    2016-09-28

    Stable metal (e.g. Li, Mg, Ca, Fe, Cu, Zn, and Mo) and metalloid (B, Si, Ge) isotope ratio systems have emerged as geochemical tracers to fingerprint distinct physicochemical reactions. These systems are relevant to many Earth Science questions. The benefit of in situ microscale analysis using laser ablation (LA) over bulk sample analysis is to use the spatial context of different phases in the solid sample to disclose the processes that govern their chemical and isotopic compositions. However, there is a lack of in situ analytical routines to obtain a samples' stable isotope ratio together with its chemical composition. Here, we evaluate two novel analytical routines for the simultaneous determination of the chemical and Si stable isotope composition (δ{sup 30}Si) on the micrometre scale in geological samples. In both routines, multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) is combined with femtosecond-LA, where stable isotope ratios are corrected for mass bias using standard-sample-bracketing with matrix-independent calibration. The first method is based on laser ablation split stream (LASS), where the laser aerosol is split and introduced simultaneously into both the MC-ICP-MS and a quadrupole ICP-MS. The second method is based on optical emission spectroscopy using direct observation of the MC-ICP-MS plasma (LA-MC-ICP-MS|OES). Both methods are evaluated using international geological reference materials. Accurate and precise Si isotope ratios were obtained with an uncertainty typically better than 0.23‰, 2SD, δ{sup 30}Si. With both methods major element concentrations (e.g., Na, Al, Si, Mg, Ca) can be simultaneously determined. However, LASS-ICP-MS is superior over LA-MC-ICP-MS|OES, which is limited by its lower sensitivity. Moreover, LASS-ICP-MS offers trace element analysis down to the μg g{sup −1}-range for more than 28 elements due to lower limits of detection, and with typical uncertainties better than 15%. For in situ

  13. Development of routines for simultaneous in situ chemical composition and stable Si isotope ratio analysis by femtosecond laser ablation inductively coupled plasma mass spectrometry

    International Nuclear Information System (INIS)

    Frick, Daniel A.; Schuessler, Jan A.; Blanckenburg, Friedhelm von

    2016-01-01

    Stable metal (e.g. Li, Mg, Ca, Fe, Cu, Zn, and Mo) and metalloid (B, Si, Ge) isotope ratio systems have emerged as geochemical tracers to fingerprint distinct physicochemical reactions. These systems are relevant to many Earth Science questions. The benefit of in situ microscale analysis using laser ablation (LA) over bulk sample analysis is to use the spatial context of different phases in the solid sample to disclose the processes that govern their chemical and isotopic compositions. However, there is a lack of in situ analytical routines to obtain a samples' stable isotope ratio together with its chemical composition. Here, we evaluate two novel analytical routines for the simultaneous determination of the chemical and Si stable isotope composition (δ 30 Si) on the micrometre scale in geological samples. In both routines, multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) is combined with femtosecond-LA, where stable isotope ratios are corrected for mass bias using standard-sample-bracketing with matrix-independent calibration. The first method is based on laser ablation split stream (LASS), where the laser aerosol is split and introduced simultaneously into both the MC-ICP-MS and a quadrupole ICP-MS. The second method is based on optical emission spectroscopy using direct observation of the MC-ICP-MS plasma (LA-MC-ICP-MS|OES). Both methods are evaluated using international geological reference materials. Accurate and precise Si isotope ratios were obtained with an uncertainty typically better than 0.23‰, 2SD, δ 30 Si. With both methods major element concentrations (e.g., Na, Al, Si, Mg, Ca) can be simultaneously determined. However, LASS-ICP-MS is superior over LA-MC-ICP-MS|OES, which is limited by its lower sensitivity. Moreover, LASS-ICP-MS offers trace element analysis down to the μg g −1 -range for more than 28 elements due to lower limits of detection, and with typical uncertainties better than 15%. For in situ

  14. Neutron activation analysis of Permian-Triassic boundary layer samples at the Selong Site in China

    International Nuclear Information System (INIS)

    Miyamoto, Y.; Sakamoto, K.; Mingqing, W.

    1997-01-01

    Thirty samples from a limestone stratum across the Permian-Triassic (P-Tr) boundary layer in China were analyzed for 30 elements by instrumental neutron activation analysis, wavelength dispersive X-ray fluorescence and ICP-MS, and also for mineral compositions with a powder X-ray diffractometer. The depth profile was found to indicate a sudden change of elemental and mineral compositions across the P-Tr boundary. Also the profile showed several peaks in elemental concentrations in the lower Permian layered samples as well as in the overlying Triassic strata, which are associated with the change of mineral compositions. Elemental profiles were found to be classified into 4 groups and to give some insights in the geochemical records. Ir is far less abundant (0.1 ppt) compared with that of the K-T boundaries (10 ppb), and the Ir/Co ratio is outside the K-T and Cl chondrite trends. This change of elementary profile is suggestive of the internal causes rather than the external ones such as an asteroid impact for the mass extinction at the P-Tr boundary. (author)

  15. ICP-MS with hexapole collision cell for isotope ratio measurements of Ca, Fe, and Se.

    Science.gov (United States)

    Boulyga, S F; Becker, J S

    2001-07-01

    To avoid mass interferences on analyte ions caused by argon ions and argon molecular ions via reactions with collision gases, an rf hexapole filled with helium and hydrogen has been used in inductively coupled plasma mass spectrometry (ICP-MS), and its performance has been studied. Up to tenfold improvement in sensitivity was observed for heavy elements (m > 100 u), because of better ion transmission through the hexapole ion guide. A reduction of argon ions Ar+ and the molecular ions of argon ArX+ (X = O, Ar) by up to three orders of magnitude was achieved in a hexapole collision cell of an ICP-MS ("Platform ICP", Micromass, Manchester, UK) as a result of gas-phase reactions with hydrogen when the hexapole bias (HB) was set to 0 V; at an HB of 1.6 V argon, and argon-based ions of masses 40 u, 56 u, and 80 u, were reduced by approximately four, two, and five orders of magnitude, respectively. The signal-to-noise ratio 80Se/ 40Ar2+ was improved by more than five orders of magnitude under optimized experimental conditions. Dependence of mass discrimination on collision-cell properties was studied in the mass range 10 u (boron) to 238 u (uranium). Isotopic analysis of the elements affected by mass-spectrometric interference, Ca, Fe, and Se, was performed using a Meinhard nebulizer and an ultrasonic nebulizer (USN). The measured isotope ratios were comparable with tabulated values from IUPAC. Precision of 0.26%, 0.19%, and 0.12%, respectively, and accuracy of 0.13% 0.25%, and 0.92%, respectively, was achieved for isotope ratios 44Ca/ 40Ca and 56Fe/57Fe in 10 microg L(-1) solution nebulized by means of a USN and for 78Se/80Se in 100 microg L(-1) solution nebulized by means of a Meinhard nebulizer.

  16. Biogenic volatile organic compound emissions from senescent maize leaves and a comparison with other leaf developmental stages

    Science.gov (United States)

    Mozaffar, A.; Schoon, N.; Bachy, A.; Digrado, A.; Heinesch, B.; Aubinet, M.; Fauconnier, M.-L.; Delaplace, P.; du Jardin, P.; Amelynck, C.

    2018-03-01

    Plants are the major source of Biogenic Volatile Organic Compounds (BVOCs) which have a large influence on atmospheric chemistry and the climate system. Therefore, understanding of BVOC emissions from all abundant plant species at all developmental stages is very important. Nevertheless, investigations on BVOC emissions from even the most widespread agricultural crop species are rare and mainly confined to the healthy green leaves. Senescent leaves of grain crop species could be an important source of BVOCs as almost all the leaves senesce on the field before being harvested. For these reasons, BVOC emission measurements have been performed on maize (Zea mays L.), one of the most cultivated crop species in the world, at all the leaf developmental stages. The measurements were performed in controlled environmental conditions using dynamic enclosures and proton transfer reaction mass spectrometry (PTR-MS). The main compounds emitted by senescent maize leaves were methanol (31% of the total cumulative BVOC emission on a mass of compound basis) and acetic acid (30%), followed by acetaldehyde (11%), hexenals (9%) and m/z 59 compounds (acetone/propanal) (7%). Important differences were observed in the temporal emission profiles of the compounds, and both yellow leaves during chlorosis and dry brown leaves after chlorosis were identified as important senescence-related BVOC sources. Total cumulative BVOC emissions from senescent maize leaves were found to be among the highest for senescent Poaceae plant species. BVOC emission rates varied strongly among the different leaf developmental stages, and senescent leaves showed a larger diversity of emitted compounds than leaves at earlier stages. Methanol was the compound with the highest emissions for all the leaf developmental stages and the contribution from the young-growing, mature, and senescent stages to the total methanol emission by a typical maize leaf was 61, 13, and 26%, respectively. This study shows that BVOC

  17. Mid-Infrared Emission Features in the ISM: Feature-to-Features Flux Ratios

    Science.gov (United States)

    Lu, N. Y.

    1998-01-01

    Using a limited, but representative sample of sources in the ISM of our Galaxy with published spectra from the Infrared Space Observatory, we analyze flux ratios between the major mid-IR emission features (EFs) centered around 6.2, 7.7, 8.6 and 11.3 mu, respectively.

  18. Monoterpene separation by coupling proton transfer reaction time-of-flight mass spectrometry with fastGC.

    Science.gov (United States)

    Materić, Dušan; Lanza, Matteo; Sulzer, Philipp; Herbig, Jens; Bruhn, Dan; Turner, Claire; Mason, Nigel; Gauci, Vincent

    2015-10-01

    Proton transfer reaction mass spectrometry (PTR-MS) is a well-established technique for real-time analysis of volatile organic compounds (VOCs). Although it is extremely sensitive (with sensitivities of up to 4500 cps/ppbv, limits of detection monoterpenes, which belong to the most important plant VOCs, still cannot be distinguished so more traditional technologies, such as gas chromatography mass spectrometry (GC-MS), have to be utilised. GC-MS is very time consuming (up to 1 h) and cannot be used for real-time analysis. Here, we introduce a sensitive, near-to-real-time method for plant monoterpene research-PTR-MS coupled with fastGC. We successfully separated and identified six of the most abundant monoterpenes in plant studies (α- and β-pinenes, limonene, 3-carene, camphene and myrcene) in less than 80 s, using both standards and conifer branch enclosures (Norway spruce, Scots pine and black pine). Five monoterpenes usually present in Norway spruce samples with a high abundance were separated even when the compound concentrations were diluted to 20 ppbv. Thus, fastGC-PTR-ToF-MS was shown to be an adequate one-instrument solution for plant monoterpene research.

  19. The ratio of effective building height to street width governs dispersion of local vehicle emissions

    Science.gov (United States)

    Schulte, Nico; Tan, Si; Venkatram, Akula

    2015-07-01

    Analysis of data collected in street canyons located in Hanover, Germany and Los Angeles, USA, suggests that street-level concentrations of vehicle-related pollutants can be estimated with a model that assumes that vertical turbulent transport of emissions dominates the governing processes. The dispersion model relates surface concentrations to traffic flow rate, the effective aspect ratio of the street, and roof level turbulence. The dispersion model indicates that magnification of concentrations relative to those in the absence of buildings is most sensitive to the aspect ratio of the street, which is the ratio of the effective height of the buildings on the street to the width of the street. This result can be useful in the design of transit oriented developments that increase building density to reduce emissions from transportation.

  20. Determination of 129I/127I isotope ratios in liquid solutions and environmental soil samples by ICP-MS with hexapole collision cell

    OpenAIRE

    Izmer, A. V.; Boulyga, S. F.; Becker, J. S.

    2003-01-01

    The determination of I-129 in environmental samples at ultratrace levels is very difficult by ICP-MS due to a high noise caused by Xe impurities in argon plasma gas (interference of Xe-129(+)), possible (IH2+)-I-127 interference and an insufficient abundance ratio sensitivity of the ICP mass spectrometer for I-129/I-127 isotope ratio measurement. A sensitive, powerful and fast analytical technique for iodine isotope ratio measurements in aqueous solutions and contaminated soil samples directl...

  1. A novel fast gas chromatography method for higher time resolution measurements of speciated monoterpenes in air

    Science.gov (United States)

    Jones, C. E.; Kato, S.; Nakashima, Y.; Kajii, Y.

    2014-05-01

    ~30 km west of central Tokyo, Japan, the Fast-GC limit of detection with respect to monoterpenes was 4-5 ppt, and the agreement between Fast-GC and PTR-MS derived total monoterpene mixing ratios was consistent with previous GC/PTR-MS comparisons. The measurement uncertainties associated with the Fast-GC quantification of monoterpenes are ≤ 12%, while larger uncertainties (up to ~25%) are associated with the OBVOC and sesquiterpene measurements.

  2. A novel Fast Gas Chromatography based technique for higher time resolution measurements of speciated monoterpenes in air

    Science.gov (United States)

    Jones, C. E.; Kato, S.; Nakashima, Y.; Kajii, Y.

    2013-12-01

    Fast-GC limit of detection with respect to monoterpenes was 4-5 ppt, and the agreement between Fast-GC and PTR-MS derived total monoterpene mixing ratios was consistent with previous GC/PTR-MS comparisons. The measurement uncertainties associated with the Fast-GC quantification of monoterpenes are ≤ 10%, while larger uncertainties (up to ~ 25%) are associated with the OBVOC and sesquiterpene measurements.

  3. Rapid age determination of oysters using LA-ICP-MS line scans of shell Mg/Ca ratios

    Science.gov (United States)

    Gillikin, D. P.; Durham, S. R.; Goodwin, D. H.

    2016-02-01

    Magnesium to calcium (Mg/Ca) ratios exhibit a strong temperature dependence in foraminifera and corals, but not in bivalve mollusks. Various studies have reported Mg/Ca-temperature relationships with R2 values ranging from 0.3 to 0.8 and significantly different relationships for bivalves growing at different salinities. However, this poor temperature correlation does not render Mg/Ca data useless. A weak temperature dependence would allow time (seasons and years) to be determined along the growth axis of shells. This would provide information about age, growth rate and also allow other proxies to be aligned with time. Typically, oxygen isotopes (δ18O) are used to age shells without clear periodic growth lines, which is time consuming and expensive. Line scans using laser ablation systems can cover several centimeters of shell in a few minutes. We test this method on the resilifer of two oyster species (Crassostrea gigas and C. virginica) using a 193 nm Laser-Ablation-ICP-MS. Living oysters were collected from San Francisco Bay, North Carolina, South Carolina, and the Gulf of Mexico; fossil shells (Pleistocene) were also collected in South Carolina. Shells were sampled for δ18O values and Mg/Ca ratios. We use annual cycles in δ18O values to confidently determine age, then apply the Mg/Ca technique. Shells of both species exhibit annual cyclicity in Mg/Ca ratios using spot and line scan laser sampling, which matche the seasonal cyclicity determined using δ18O values. Results show a good correlation between ages determined using the different methods. We conclude that LA-ICP-MS line scans offer a rapid and inexpensive technique for determining age, growth rate, and timing of shell growth in oyster reslifers.

  4. Real-time analysis of organic compounds in ship engine aerosol emissions using resonance-enhanced multiphoton ionisation and proton transfer mass spectrometry.

    Science.gov (United States)

    Radischat, Christian; Sippula, Olli; Stengel, Benjamin; Klingbeil, Sophie; Sklorz, Martin; Rabe, Rom; Streibel, Thorsten; Harndorf, Horst; Zimmermann, Ralf

    2015-08-01

    Organic combustion aerosols from a marine medium-speed diesel engine, capable to run on distillate (diesel fuel) and residual fuels (heavy fuel oil), were investigated under various operating conditions and engine parameters. The online chemical characterisation of the organic components was conducted using a resonance-enhanced multiphoton ionisation time-of-flight mass spectrometer (REMPI TOF MS) and a proton transfer reaction-quadrupole mass spectrometer (PTR-QMS). Oxygenated species, alkenes and aromatic hydrocarbons were characterised. Especially the aromatic hydrocarbons and their alkylated derivatives were very prominent in the exhaust of both fuels. Emission factors of known health-hazardous compounds (e.g. mono- and poly-aromatic hydrocarbons) were calculated and found in higher amounts for heavy fuel oil (HFO) at typical engine loadings. Lower engine loads lead in general to increasing emissions for both fuels for almost every compound, e.g. naphthalene emissions varied for diesel fuel exhaust between 0.7 mg/kWh (75 % engine load, late start of injection (SOI)) and 11.8 mg/kWh (10 % engine load, late SOI) and for HFO exhaust between 3.3 and 60.5 mg/kWh, respectively. Both used mass spectrometric techniques showed that they are particularly suitable methods for online monitoring of combustion compounds and very helpful for the characterisation of health-relevant substances. Graphical abstract Three-dimensional REMPI data of organic species in diesel fuel and heavy fuel oil exhaust.

  5. ICP-MS with hexapole collision cell for isotope ratio measurements of Ca, Fe, and Se

    Energy Technology Data Exchange (ETDEWEB)

    Boulyga, S.F. [Radiation Physics and Chemistry Problems Inst., Minsk (Belarus); Becker, J.S. [Central Department for Analytical Chemistry, Research Centre Juelich (Germany)

    2001-07-01

    To avoid mass interferences on analyte ions caused by argon ions and argon molecular ions via reactions with collision gases, an rf hexapole filled with helium and hydrogen has been used in inductively coupled plasma mass spectrometry (ICP-MS), and its performance has been studied. Up to tenfold improvement in sensitivity was observed for heavy elements (m > 100 u), because of better ion transmission through the hexapole ion guide. A reduction of argon ions Ar{sup +} and the molecular ions of argon ArX{sup +} (X = O, Ar) by up to three orders of magnitude was achieved in a hexapole collision cell of an ICP-MS (''Platform ICP'', Micromass, Manchester, UK) as a result of gas-phase reactions with hydrogen when the hexapole bias (HB) was set to 0 V; at an HB of 1.6 V argon, and argon-based ions of masses 40 u, 56 u, and 80 u, were reduced by approximately four, two, and five orders of magnitude, respectively. The signal-to-noise ratio {sup 80}Se/ {sup 40}Ar{sub 2}{sup +} was improved by more than five orders of magnitude under optimized experimental conditions. Dependence of mass discrimination on collision-cell properties was studied in the mass range 10 u (boron) to 238 u (uranium). Isotopic analysis of the elements affected by mass-spectrometric interference, Ca, Fe, and Se, was performed using a Meinhard nebulizer and an ultrasonic nebulizer (USN). The measured isotope ratios were comparable with tabulated values from IUPAC. Precision of 0.26%, 0.19%, and 0.12%, respectively, and accuracy of 0.13% 0.25%, and 0.92%, respectively, was achieved for isotope ratios {sup 44}Ca/ {sup 40}Ca and {sup 56}Fe/{sup 57}Fe in 10 {mu}g L{sup -1} solution nebulized by means of a USN and for {sup 78}Se/{sup 80}Se in 100 {mu}g L{sup -1} solution nebulized by means of a Meinhard nebulizer. (orig.)

  6. EFFECT OF COMPRESSION RATIO ON ENERGY AND EMISSION OF VCR DIESEL ENGINE FUELLED WITH DUAL BLENDS OF BIODIESEL

    Directory of Open Access Journals (Sweden)

    R. D. EKNATH

    2014-10-01

    Full Text Available In recent 10 years biodiesel fuel was studied extensively as an alternative fuel. Most of researchers reported performance and emission of biodiesel and their blends with constant compression ratio. Also all the research was conducted with use of single biodiesel and its blend. Few reports are observed with the use of variable compression ratio and blends of more than one biodiesel. Main aim of the present study is to analyse the effect of compression ratio on the performance and emission of dual blends of biodiesel. In the present study Blends of Jatropha and Karanja with Diesel fuel was tested on single cylinder VCR DI diesel engine for compression ratio 16 and 18. High density of biodiesel fuel causes longer delay period for Jatropha fuel was observed compare with Karanja fuel. However blending of two biodiesel K20J40D results in to low mean gas temperature which is the main reason for low NOx emission.

  7. CO2 emissions embodied in China-US trade: Input-output analysis based on the emergy/dollar ratio

    International Nuclear Information System (INIS)

    Du Huibin; Guo Jianghong; Mao Guozhu; Smith, Alexander M.; Wang Xuxu; Wang, Yuan

    2011-01-01

    To gain insight into changes in CO 2 emissions embodied in China-US trade, an input-output analysis based on the emergy/dollar ratio (EDR) is used to estimate embodied CO 2 emissions; a structural decomposition analysis (SDA) is employed to analyze the driving factors for changes in CO 2 emissions embodied in China's exports to the US during 2002-2007. The results of the input-output analysis show that net export of CO 2 emissions increased quickly from 2002 to 2005 but decreased from 2005 to 2007. These trends are due to a reduction in total CO 2 emission intensity, a decrease in the exchange rate, and small imports of embodied CO 2 emissions. The results of the SDA demonstrate that total export volume was the largest driving factor for the increase in embodied CO 2 emissions during 2002-2007, followed by intermediate input structure. Direct CO 2 emissions intensity had a negative effect on changes in embodied CO 2 emissions. The results suggest that China should establish a framework for allocating emission responsibilities, enhance energy efficiency, and improve intermediate input structure. - Highlights: → An input-output analysis based on the emergy/dollar ratio estimated embodied CO 2 . → A structural decomposition analysis analyzed the driving factors. → Net export of CO 2 increased from 2002 to 2005 but decreased from 2005 to 2007. → Total export volume was the largest driving factor. → A framework for allocating emission responsibilities.

  8. A new method of organizing spectral line intensity ratio fluctuations of auroral emissions

    International Nuclear Information System (INIS)

    Thelin, B.

    1986-02-01

    In this paper a new kind of linearization effect between the atmospheric auroral emissions is presented. The same kind of linearization effect has previously been found in nightglow emissions from photometer measurements and in the spectrochemical field from studies of optical light sources. Linear graphs have been obtained for atomic spectral lines and vibrational bandspectra when the spectral line ratio fluctuations were plotted versus the photon energies of these emissions. This new effect has been studied with a spectrophotometer in auroral emissions, where linear graphs have been obtained on different auroral occasions. By doing such studies of auroral light it is possible to see the importance of the inelastic scattering cross section between electrons - atoms and electrons - molecules. In this way it has shown to be possible to determine the mean energy of the interacting thermal electrons that are active in the different auroral phases. (author)

  9. A statistical analysis of volatile organic compounds observed during the TEXAQS2000 air quality study at LaPorte, Tx, using proton-transfer-reaction mass spectrometry

    International Nuclear Information System (INIS)

    Kuster, B.; Williams, E.; Fehsenfeld, F.; Jobson, T.; Fall, R.; Lindinger, W.; Karl, T.

    2002-01-01

    Statistical analysis of online VOC measurements obtained by proton-transfer-reaction mass spectrometry (PTR-MS) during the TEXAQS2000 intensive period is presented. The experiment was based at the La Porte site, near the Houston ship channel (HSC), and deployed for continuous long-term monitoring. Multivariate techniques helped to identify various VOC sources in the vicinity of HSC and distinguish between different anthropogenic emissions. An assessment is given of the selectivity and interpretation of mass scans from this online technique in complex urban and industrial VOC matrix. (author)

  10. Effect of C/N ratio, aeration rate and moisture content on ammonia and greenhouse gas emission during the composting.

    Science.gov (United States)

    Jiang, Tao; Schuchardt, Frank; Li, Guoxue; Guo, Rui; Zhao, Yuanqiu

    2011-01-01

    Gaseous emission (N2O, CH4 and NH3) from composting can be an important source of anthropogenic greenhouse gas and air pollution. A laboratory scale orthogonal experiment was conducted to estimate the effects of C/N ratio, aeration rate and initial moisture content on gaseous emission during the composting of pig faeces from Chinese Ganqinfen system. The results showed that about 23.9% to 45.6% of total organic carbon (TOC) was lost in the form of CO2 and 0.8% to 7.5% of TOC emitted as CH4. Most of the nitrogen was lost in the form of NH3, which account for 9.6% to 32.4% of initial nitrogen. N2O was also an important way of nitrogen losses and 1.5% to 7.3% of initial total nitrogen was lost as it. Statistic analysis showed that the aeration rate is the most important factor which could affect the NH3 (p = 0.0189), CH4 (p = 0.0113) and N2O (p = 0.0493) emissions significantly. Higher aeration rates reduce the CH4 emission but increase the NH3 and N2O losses. C/N ratio could affect the NH3 (p = 0.0442) and CH4 (p = 0.0246) emissions significantly, but not the N2O. Lower C/N ratio caused higher NH3 and CH4 emissions. The initial moisture content can not influence the gaseous emission significantly. Most treatments were matured after 37 days, except a trial with high moisture content and a low C/N ratio.

  11. BVOC emission in Norway spruce: the effect of stand structure, high temperature and ozone levels.

    Science.gov (United States)

    Pallozzi, Emanuele; Guidolotti, Gabriele; Večeřová, Kristýna; Esposito, Raffaela; Lusini, Ilaria; Juráň, Stanislav; Urban, Otmar; Calfapietra, Carlo

    2015-04-01

    Norway spruce (Picea abies L.) is a widely distributed conifer species in the boreal zone and mountain areas of central Europe and is a moderate emitter of volatile organic compounds (BVOC). Although the vaporization and diffusion processes from resin ducts were generally considered to be the main processes for monoterpene emissions in conifers, recently it has been showed that a significant portion (up to one third) of monoterpene emissions of Norway spruce can originate from novel biosynthesis, thus depending on photosynthetic processes. For this reason, both biosynthesis and emission are strongly influenced by the environment and the stand structure. They increase with both increasing light and temperature during the warmer periods, although those are the periods with the higher ozone concentration that usually act as an inhibitor of both assimilation and isoprenoids synthesis and emission. On the other hand, stand structure can play an important role, because the photosynthetic capacity is influenced by temperature and light conditions through the canopy. In order to assess the effects of stand structure, temperature and ozone on isoprenoids emission of Norway spruce we carried out field and laboratory experiments. In the experimental field campaigns we measured: assimilation and BVOC emission from needles of sun and shade layers within the canopy of the spruce forest present at the Bily Kriz experimental research site (Moravian-Silesian Beskydy Mountains, 49° 33' N, 18° 32' E, NE of Czech Republic, 908 m a.s.l.). Moreover in the same layers we measured continuously concentration of BVOCs in the air using a PTR-TOF-MS. In laboratory we analyzed the effects of short-term exposure to high temperature and high ozone concentrations on branches of spruce trees collected at the Bily Kriz experimental research site. Preliminary results show that in Norway spruce both stand structure and environmental conditions influenced the gas exchange and BVOC emission rates

  12. The co-feature ratio, a novel method for the measurement of chromatographic and signal selectivity in LC-MS-based metabolomics

    International Nuclear Information System (INIS)

    Elmsjö, Albert; Haglöf, Jakob; Engskog, Mikael K.R.; Nestor, Marika; Arvidsson, Torbjörn; Pettersson, Curt

    2017-01-01

    Evaluation of analytical procedures, especially in regards to measuring chromatographic and signal selectivity, is highly challenging in untargeted metabolomics. The aim of this study was to suggest a new straightforward approach for a systematic examination of chromatographic and signal selectivity in LC-MS-based metabolomics. By calculating the ratio between each feature and its co-eluting features (the co-features), a measurement of the chromatographic selectivity (i.e. extent of co-elution) as well as the signal selectivity (e.g. amount of adduct formation) of each feature could be acquired, the co-feature ratio. This approach was used to examine possible differences in chromatographic and signal selectivity present in samples exposed to three different sample preparation procedures. The capability of the co-feature ratio was evaluated both in a classical targeted setting using isotope labelled standards as well as without standards in an untargeted setting. For the targeted analysis, several metabolites showed a skewed quantitative signal due to poor chromatographic selectivity and/or poor signal selectivity. Moreover, evaluation of the untargeted approach through multivariate analysis of the co-feature ratios demonstrated the possibility to screen for metabolites displaying poor chromatographic and/or signal selectivity characteristics. We conclude that the co-feature ratio can be a useful tool in the development and evaluation of analytical procedures in LC-MS-based metabolomics investigations. Increased selectivity through proper choice of analytical procedures may decrease the false positive and false negative discovery rate and thereby increase the validity of any metabolomic investigation. - Highlights: • The co-feature ratio (CFR) is introduced. • CFR measures chromatographic and signal selectivity of a feature. • CFR can be used for evaluating experimental procedures in metabolomics. • CFR can aid in locating features with poor selectivity.

  13. The co-feature ratio, a novel method for the measurement of chromatographic and signal selectivity in LC-MS-based metabolomics

    Energy Technology Data Exchange (ETDEWEB)

    Elmsjö, Albert, E-mail: Albert.Elmsjo@farmkemi.uu.se [Department of Medicinal Chemistry, Division of Analytical Pharmaceutical Chemistry, Uppsala University (Sweden); Haglöf, Jakob; Engskog, Mikael K.R. [Department of Medicinal Chemistry, Division of Analytical Pharmaceutical Chemistry, Uppsala University (Sweden); Nestor, Marika [Department of Immunology, Genetics and Pathology, Uppsala University (Sweden); Arvidsson, Torbjörn [Department of Medicinal Chemistry, Division of Analytical Pharmaceutical Chemistry, Uppsala University (Sweden); Medical Product Agency, Uppsala (Sweden); Pettersson, Curt [Department of Medicinal Chemistry, Division of Analytical Pharmaceutical Chemistry, Uppsala University (Sweden)

    2017-03-01

    Evaluation of analytical procedures, especially in regards to measuring chromatographic and signal selectivity, is highly challenging in untargeted metabolomics. The aim of this study was to suggest a new straightforward approach for a systematic examination of chromatographic and signal selectivity in LC-MS-based metabolomics. By calculating the ratio between each feature and its co-eluting features (the co-features), a measurement of the chromatographic selectivity (i.e. extent of co-elution) as well as the signal selectivity (e.g. amount of adduct formation) of each feature could be acquired, the co-feature ratio. This approach was used to examine possible differences in chromatographic and signal selectivity present in samples exposed to three different sample preparation procedures. The capability of the co-feature ratio was evaluated both in a classical targeted setting using isotope labelled standards as well as without standards in an untargeted setting. For the targeted analysis, several metabolites showed a skewed quantitative signal due to poor chromatographic selectivity and/or poor signal selectivity. Moreover, evaluation of the untargeted approach through multivariate analysis of the co-feature ratios demonstrated the possibility to screen for metabolites displaying poor chromatographic and/or signal selectivity characteristics. We conclude that the co-feature ratio can be a useful tool in the development and evaluation of analytical procedures in LC-MS-based metabolomics investigations. Increased selectivity through proper choice of analytical procedures may decrease the false positive and false negative discovery rate and thereby increase the validity of any metabolomic investigation. - Highlights: • The co-feature ratio (CFR) is introduced. • CFR measures chromatographic and signal selectivity of a feature. • CFR can be used for evaluating experimental procedures in metabolomics. • CFR can aid in locating features with poor selectivity.

  14. Effect of compression ratio, equivalence ratio and engine speed on the performance and emission characteristics of a spark ignition engine using hydrogen as a fuel

    Energy Technology Data Exchange (ETDEWEB)

    Sadiq Al-Baghdadi, M.A.R. [University of Babylon (Iraq). Dept. of Mechanical Engineering

    2004-12-01

    The present energy situation has stimulated active research interest in non-petroleum and non-polluting fuels, particularly for transportation, power generation, and agricultural sectors. Researchers have found that hydrogen presents the best and an unprecedented solution to the energy crises and pollution problems, due to its superior combustion qualities and availability. This paper discusses analytically and provides data on the effect of compression ratio, equivalence ratio and engine speed on the engine performance, emissions and pre-ignition limits of a spark ignition engine operating on hydrogen fuel. These data are important in order to understand the interaction between engine performance and emission parameters, which will help engine designers when designing for hydrogen. (author)

  15. Trans-boundary movement of mercury in the Northeast Asian region predicted by CAMQ-Hg from anthropogenic emissions distribution

    Science.gov (United States)

    Sung, Jin-Ho; Roy, Debananda; Oh, Joo-Sung; Back, Seung-Ki; Jang, Ha-Na; Kim, Seong-Heon; Seo, Yong-Chil; Kim, Jeong-Hun; Lee, Chong Bum; Han, Young-Ji

    2018-05-01

    The percentage contribution of trans-boundary mercury (Hg) from China at different locations in South Korea was estimated from Hg anthropogenic emission distributions using the Hg dispersion model, CMAQ-Hg. This investigation quantifies the trans-boundary Hg emissions as contribution ratios. In addition, the long-range transportation frequency is also calculated, to verify inflow cases from China. The seasonal distribution of the Hg contribution ratio was found to be highest in winter (40%), followed by fall (16%). Seasonal observations of Hg inflow frequencies were estimated as 40%, 25%, 21%, and 4% in winter, fall, summer, and spring, respectively, at the same location. Such results would be produced by the wind generally blowing from the west and north-west with a speed of 5.0 m/s and 4.5 m/s, respectively, during winter and fall, around the study area. This study made an effort to quantify the trans-boundary Hg transport and to plot Hg anthropogenic emissions distribution in the region.

  16. An intercomparison of airborne VOC measurements

    International Nuclear Information System (INIS)

    Wisthaler, A.; Hansel, A.; Fall, R.

    2002-01-01

    Full text: During the Texas Air Quality Study (TexAQS) 2000 ambient air samples were analyzed on-board the NSF/NCAR ELECTRA research aircraft by two VOC measurement techniques: 1) an in-situ gas chromatograph named TACOH (Tropospheric Airborne Chromatograph for Oxy-hydrocarbons and Hydrocarbons), operated by NOAA' Aeronomy Laboratory, and 2) a chemical ionization mass spectrometer named PTR-MS (Proton-Transfer-Reaction Mass Spectrometer) and operated by the University of Innsbruck. The sample protocols were quite different for the two methods: the TACOH system collected air samples for 15-60 sec (depending upon altitude) every 15 min, the PTR-MS system monitored selected VOCs on a time-shared basis for 2 sec respectively, once every 4-20 sec, depending upon the number of monitored species. Simultaneous measurements of acetaldehyde, isoprene, the sum* of acetone and propanal, the sum* of methyl vinyl ketone and methacrolein (* PTR-MS does not distinguish between isobaric species) and toluene show good agreement despite being performed in the complex and highly polluted Houston air matrix. (author)

  17. The impact of power market structure on the pass-through of CO2 emissions trading costs to electricity prices. A theoretical approach

    International Nuclear Information System (INIS)

    Sijm, J.; Chen, Yihsu; Hobbs, B.F.

    2009-06-01

    This paper analyses the impact of power market structure on the pass-through rate (PTR) of CO2 emissions trading costs on electricity prices from a theoretical point of view, including graphical illustrations and mathematical proofs. Market structure refers in particular to the number of firms active in the market as well as to the shape of the power demand and supply curves. In addition, it analyses the impact of other power market related factors on the PTR of carbon costs to electricity prices, notably the impact of ET-induced changes in the merit order of power generation technologies or the impact of pursuing other market strategies besides maximising generators' profits, such as maximising market shares or sales revenues of power companies. It shows that each of these factors can have a significant impact on the rate of passing-through carbon costs to electricity prices

  18. The impact of power market structure on the pass-through of CO2 emissions trading costs to electricity prices. A theoretical approach

    Energy Technology Data Exchange (ETDEWEB)

    Sijm, J. [ECN Policy Studies, Petten (Netherlands); Chen, Yihsu [Merced School of Engineering, University of California, Merced, CA (United States); Hobbs, B.F. [Department of Geography and Environmental Engineering, Johns Hopkins University, Baltimore, Maryland (United States)

    2009-06-15

    This paper analyses the impact of power market structure on the pass-through rate (PTR) of CO2 emissions trading costs on electricity prices from a theoretical point of view, including graphical illustrations and mathematical proofs. Market structure refers in particular to the number of firms active in the market as well as to the shape of the power demand and supply curves. In addition, it analyses the impact of other power market related factors on the PTR of carbon costs to electricity prices, notably the impact of ET-induced changes in the merit order of power generation technologies or the impact of pursuing other market strategies besides maximising generators' profits, such as maximising market shares or sales revenues of power companies. It shows that each of these factors can have a significant impact on the rate of passing-through carbon costs to electricity prices.

  19. Performance and emission characteristics of a turbocharged CNG engine fueled by hydrogen-enriched compressed natural gas with high hydrogen ratio

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Fanhua; Wang, Mingyue; Jiang, Long; Chen, Renzhe; Deng, Jiao; Naeve, Nashay; Zhao, Shuli [State Key Laboratory of Automotive Safety and Energy Tsinghua University, Beijing 100084 (China)

    2010-06-15

    This paper investigates the effect of high hydrogen volumetric ratio of 55% on performance and emission characteristics in a turbocharged lean burn natural gas engine. The experimental data was conducted under various operating conditions including different spark timing, excess air ratio (lambda), and manifold pressure. It is found that the addition of hydrogen at a high volumetric ratio could significantly extend the lean burn limit, improve the engine lean burn ability, decrease burn duration, and yield higher thermal efficiency. The CO, CH{sub 4} emissions were reduced and NO{sub x} emission could be kept an acceptable low level with high hydrogen content under lean burn conditions when ignition timing were optimized. (author)

  20. Asymmetry of Peak Thicknesses between the Superior and Inferior Retinal Nerve Fiber Layers for Early Glaucoma Detection: A Simple Screening Method.

    Science.gov (United States)

    Bae, Hyoung Won; Lee, Sang Yeop; Kim, Sangah; Park, Chan Keum; Lee, Kwanghyun; Kim, Chan Yun; Seong, Gong Je

    2018-01-01

    To assess whether the asymmetry in the peripapillary retinal nerve fiber layer (pRNFL) thickness between superior and inferior hemispheres on optical coherence tomography (OCT) is useful for early detection of glaucoma. The patient population consisted of Training set (a total of 60 subjects with early glaucoma and 59 normal subjects) and Validation set (30 subjects with early glaucoma and 30 normal subjects). Two kinds of ratios were employed to measure the asymmetry between the superior and inferior pRNFL thickness using OCT. One was the ratio of the superior to inferior peak thicknesses (peak pRNFL thickness ratio; PTR), and the other was the ratio of the superior to inferior average thickness (average pRNFL thickness ratio; ATR). The diagnostic abilities of the PTR and ATR were compared to the color code classification in OCT. Using the optimal cut-off values of the PTR and ATR obtained from the Training set, the two ratios were independently validated for diagnostic capability. For the Training set, the sensitivities/specificities of the PTR, ATR, quadrants color code classification, and clock-hour color code classification were 81.7%/93.2%, 71.7%/74.6%, 75.0%/93.2%, and 75.0%/79.7%, respectively. The PTR showed a better diagnostic performance for early glaucoma detection than the ATR and the clock-hour color code classification in terms of areas under the receiver operating characteristic curves (AUCs) (0.898, 0.765, and 0.773, respectively). For the Validation set, the PTR also showed the best sensitivity and AUC. The PTR is a simple method with considerable diagnostic ability for early glaucoma detection. It can, therefore, be widely used as a new screening method for early glaucoma. © Copyright: Yonsei University College of Medicine 2018

  1. BAT AGN Spectroscopic Survey - III. An Observed Link Between AGN Eddington Ratio and Narrow-Emission-Line Ratios

    Science.gov (United States)

    Oh, Kyuseok; Schawinski, Kevin; Koss, Michael; Trakhtenbrot, Benny; Lamperti, Isabella; Ricci, Claudio; Mushotzky, Richard; Veilleux, Sylvain; Berney, Simon; Crenshaw, D. Michael; hide

    2016-01-01

    We investigate the observed relationship between black hole mass (M(sub BH)), bolometric luminosity (L(sub bol)) and Eddington ratio (lambda(sub Edd)) with optical emission-line ratios ([N II] lambda6583/Halpha, [S II]lambda-lamda6716, 6731/Halpha, [O I] lamda6300/Halpha, [O III] lamda5007/Hbeta, [Ne III] lamda3869/Hbeta and He II lamda4686/Hbeta) of hard X-ray-selected active galactic nuclei (AGN) from the BAT AGN Spectroscopic Survey. We show that the [N II] lamda6583/Halpha ratio exhibits a significant correlation with lamda(sub Edd) (R(sub Pear) = -0.44, p-value 3 x 10(exp. -13) sigma = 0.28 dex), and the correlation is not solely driven by M(sub BH) or L(sub bol). The observed correlation between [N II] lamda6583/Halpha ratio and M(sub BH) is stronger than the correlation with L(sub bol), but both are weaker than the lamda(sub Edd) correlation. This implies that the large-scale narrow lines of AGN host galaxies carry information about the accretion state of the AGN central engine. We propose that [N II] lamda6583/Halpha is a useful indicator of Eddington ratio with 0.6 dex of rms scatter, and that it can be used to measure lambda(sub Edd) and thus M(sub BH) from the measured L(sub bol), even for high-redshift obscured AGN. We briefly discuss possible physical mechanisms behind this correlation, such as the mass-metallicity relation, X-ray heating, and radiatively driven outflows.

  2. Nitrogen removal and nitrous oxide emission in surface flow constructed wetlands for treating sewage treatment plant effluent: Effect of C/N ratios.

    Science.gov (United States)

    Li, Ming; Wu, Haiming; Zhang, Jian; Ngo, Huu Hao; Guo, Wenshan; Kong, Qiang

    2017-09-01

    In order to design treatment wetlands with maximal nitrogen removal and minimal nitrous oxide (N 2 O) emission, the effect of influent C/N ratios on nitrogen removal and N 2 O emission in surface flow constructed wetlands (SF CWs) for sewage treatment plant effluent treatment was investigated in this study. The results showed that nitrogen removal and N 2 O emission in CWs were significantly affected by C/N ratio of influent. Much higher removal efficiency of NH 4 + -N (98%) and TN (90%) was obtained simultaneously in SF CWs at C/N ratios of 12:1, and low N 2 O emission (8.2mg/m 2 /d) and the percentage of N 2 O-N emission in TN removal (1.44%) were also observed. These results obtained in this study would be utilized to determine how N 2 O fluxes respond to variations in C/N ratios and to improve the sustainability of CWs for wastewater treatment. Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. Combustion and emissions characteristics of high n-butanol/diesel ratio blend in a heavy-duty diesel engine and EGR impact

    International Nuclear Information System (INIS)

    Chen, Zheng; Wu, Zhenkuo; Liu, Jingping; Lee, Chiafon

    2014-01-01

    Highlights: • Effects of EGR on high n-butanol/diesel ratio blend (Bu40) were investigated and compared with neat diesel (Bu00). • Bu40 has higher NOx due to wider combustion high-temperature region. • Bu40 has lower soot due to local lower equivalence ratio distribution. • Bu40 has higher CO due to lower gas temperature in the late expansion process. • For Bu40, EGR reduces NOx emissions dramatically with no obvious influence on soot. - Abstract: In this work, the combustion and emission fundamentals of high n-butanol/diesel ratio blend with 40% butanol (i.e., Bu40) in a heavy-duty diesel engine were investigated by experiment and simulation at constant engine speed of 1400 rpm and an IMEP of 1.0 MPa. Additionally, the impact of EGR was evaluated experimentally and compared with neat diesel fuel (i.e., Bu00). The results show that Bu40 has higher cylinder pressure, longer ignition delay, and faster burning rate than Bu00. Compared with Bu00, moreover, Bu40 has higher NOx due to wider combustion high-temperature region, lower soot due to local lower equivalence ratio distribution, and higher CO due to lower gas temperature in the late expansion process. For Bu40, EGR reduces NOx emissions dramatically with no obvious influence on soot. Meanwhile, there is no significant change in HC and CO emissions and indicated thermal efficiency (ITE) with EGR until EGR threshold is reached. When EGR rate exceeds the threshold level, HC and CO emissions increase dramatically, and ITE decreases markedly. Compared with Bu00, the threshold of Bu40 appears at lower EGR rate. Consequently, combining high butanol/diesel ratio blend with medium EGR has the potential to achieve ultra-low NOx and soot emissions simultaneously while maintaining high thermal efficiency level

  4. 129I/127I ratios in Scottish coastal surface sea water: Geographical and temporal responses to changing emissions

    International Nuclear Information System (INIS)

    Schnabel, Christoph; Olive, Valerie; Atarashi-Andoh, Mariko; Dougans, Andrew; Ellam, Robert M.; Freeman, Stewart; Maden, Colin; Stocker, Martin; Synal, Hans-Arno; Wacker, Lukas; Xu Sheng

    2007-01-01

    This work constitutes the first survey of I isotope ratios for Scottish sea water including the first data for the west of Scotland. These data are of importance because of the proximity to the world's second largest emission source of 129 I to the sea, the Sellafield nuclear reprocessing plant, because of the increasing importance of the sea to land transfer of 129 I and also as input data for dose estimates based on this pathway of 129 I. 129 I/ 127 I ratios in SW Scotland reached 3 x 10 -6 in 2004. No strong variation of I isotope ratios was found from 2003 to 2005 in Scottish sea waters. Iodine isotope ratios increased by about a factor of 6 from 1992 to 2003 in NE Scotland, in agreement with the increase of liquid 129 I emissions from Sellafield over that time period. It is demonstrated that 129 I/ 127 I ratios agree better than 129 I concentrations for samples from similar locations taken in very close temporal proximity, indicating that this ratio is more appropriate to interpret than the radionuclide concentration

  5. Application of gas chromatography-mass spectrometry/combustion/isotope ratio mass spectrometry (GC-MS/C/IRMS) to detect the abuse of 17β-estradiol in cattle.

    Science.gov (United States)

    Janssens, Geert; Mangelinckx, Sven; Courtheyn, Dirk; Prévost, Stéphanie; De Poorter, Geert; De Kimpe, Norbert; Le Bizec, Bruno

    2013-07-31

    Although the ability to differentiate between endogenous steroids and synthetic homologues on the basis of their (13)C/(12)C isotopic ratio has been known for over a decade, this technique has been scarcely implemented for food safety purposes. In this study, a method was developed using gas chromatography-mass spectrometry/combustion/isotope ratio mass spectrometry (GC-MS/C/IRMS) to demonstrate the abuse of 17β-estradiol in cattle, by comparison of the (13)C/(12)C ratios of the main metabolite 17α-estradiol and an endogenous reference compound (ERC), 5-androstene-3β,17α-diol, in bovine urine. The intermediate precisions were determined as 0.46 and 0.26‰ for 5-androstene-3β,17α-diol and 17α-estradiol, respectively. This is, to the authors' knowledge, the first reported use of GC-MS/C/IRMS for the analysis of steroid compounds for food safety issues.

  6. ESI MS/MS Study of Calix[4]arene Derivatives and their Metal Complexes

    OpenAIRE

    Benković, Tomislav; Tomišić, Vladislav; Frkanec, Leo; Galić, Nives

    2012-01-01

    The peptidocalixarenes 1–3 bearing tryptophan, phenylglycine and leucil units at the lower rim and their complexes with alkali-metal (Li+, Na+, K+, Rb+, Cs+) and selected lanthanide cations (La3+, Ce3+, Eu3+, Yb3+) were analyzed by ESI MS. The influences of the solvent (acetonitrile, methanol, addition of formic acid or sodium acetate) and the calixarene:cation molar ratio on signal intensities were investigated. Comprehensive MS/MS analyses were performed of all singly and doubly charged ion...

  7. Performance and exhaust emission characteristics of variable compression ratio diesel engine fuelled with esters of crude rice bran oil.

    Science.gov (United States)

    Vasudeva, Mohit; Sharma, Sumeet; Mohapatra, S K; Kundu, Krishnendu

    2016-01-01

    As a substitute to petroleum-derived diesel, biodiesel has high potential as a renewable and environment friendly energy source. For petroleum importing countries the choice of feedstock for biodiesel production within the geographical region is a major influential factor. Crude rice bran oil is found to be good and viable feedstock for biodiesel production. A two step esterification is carried out for higher free fatty acid crude rice bran oil. Blends of 10, 20 and 40 % by vol. crude rice bran biodiesel are tested in a variable compression ratio diesel engine at compression ratio 15, 16, 17 and 18. Engine performance and exhaust emission parameters are examined. Cylinder pressure-crank angle variation is also plotted. The increase in compression ratio from 15 to 18 resulted in 18.6 % decrease in brake specific fuel consumption and 14.66 % increase in brake thermal efficiency on an average. Cylinder pressure increases by 15 % when compression ratio is increased. Carbon monoxide emission decreased by 22.27 %, hydrocarbon decreased by 38.4 %, carbon dioxide increased by 17.43 % and oxides of nitrogen as NOx emission increased by 22.76 % on an average when compression ratio is increased from 15 to 18. The blends of crude rice bran biodiesel show better results than diesel with increase in compression ratio.

  8. Continued increase of CFC-113a (CCl3CF3) mixing ratios in the global atmosphere: emissions, occurrence and potential sources

    Science.gov (United States)

    Adcock, Karina E.; Reeves, Claire E.; Gooch, Lauren J.; Leedham Elvidge, Emma C.; Ashfold, Matthew J.; Brenninkmeijer, Carl A. M.; Chou, Charles; Fraser, Paul J.; Langenfelds, Ray L.; Hanif, Norfazrin Mohd; O'Doherty, Simon; Oram, David E.; Ou-Yang, Chang-Feng; Moi Phang, Siew; Abu Samah, Azizan; Röckmann, Thomas; Sturges, William T.; Laube, Johannes C.

    2018-04-01

    Atmospheric measurements of the ozone-depleting substance CFC-113a (CCl3CF3) are reported from ground-based stations in Australia, Taiwan, Malaysia and the United Kingdom, together with aircraft-based data for the upper troposphere and lower stratosphere. Building on previous work, we find that, since the gas first appeared in the atmosphere in the 1960s, global CFC-113a mixing ratios have been increasing monotonically to the present day. Mixing ratios of CFC-113a have increased by 40 % from 0.50 to 0.70 ppt in the Southern Hemisphere between the end of the previously published record in December 2012 and February 2017. We derive updated global emissions of 1.7 Gg yr-1 on average between 2012 and 2016 using a two-dimensional model. We compare the long-term trends and emissions of CFC-113a to those of its structural isomer, CFC-113 (CClF2CCl2F), which still has much higher mixing ratios than CFC-113a, despite its mixing ratios and emissions decreasing since the 1990s. The continued presence of northern hemispheric emissions of CFC-113a is confirmed by our measurements of a persistent interhemispheric gradient in its mixing ratios, with higher mixing ratios in the Northern Hemisphere. The sources of CFC-113a are still unclear, but we present evidence that indicates large emissions in East Asia, most likely due to its use as a chemical involved in the production of hydrofluorocarbons. Our aircraft data confirm the interhemispheric gradient as well as showing mixing ratios consistent with ground-based observations and the relatively long atmospheric lifetime of CFC-113a. CFC-113a is the only known CFC for which abundances are still increasing substantially in the atmosphere.

  9. New application and future of ICP-MS

    International Nuclear Information System (INIS)

    Masuda, Kimihiko

    1994-01-01

    By ICP-MS, since high sensibility, multi-element rapid analysis and isotope ratio analysis can be carried out, the position as the analysis for ultra-minute amount of elements has been established. Further recently, sample feeder system has been developed, and the multi-collector type device for the purpose of high resolution type isotope ratio analysis has appeared, so the range of its application is spreading more and more. In this report, the examples of application which were able to be attained accompanying the development of these devices are introduced, and the development of the ICP-MS hereafter is described. At present, about 1000 apparatuses are in operation in the world, and the application spread to the fields of semiconductors and materials, earth science, environment, atomic energy and so on. The ICP-MS was developed for the purpose of easily carrying out spectral analysis with high sensibility by using argon ICP as the ion source and doing ion detection which is more efficient than light detection, and has lower background. The progress and the present status of the ICP-MS are reported. As the latest examples of application of the ICP-MS, the analysis of iron by quadrupole type ICP-MS, the small region measurement of solids by laser abrasion, ultra-minute amount analysis by high resolution ICP-MS, the isotope ratio measurement of lead by multi-collector type ICP-MS are reported. (K.I.)

  10. Proton transfer reaction time-of-flight mass spectrometry advancement in detection of hazardous substances

    International Nuclear Information System (INIS)

    Agarwal, B.

    2012-01-01

    Proton Transfer Reaction Mass Spectrometry (PTR-MS) is a mass spectrometric technique based on chemical ionization, which provides very rapid measurements (within seconds) of volatile organic compounds in air, usually without special sample preparation, and with a very low detection limit. The detection and study of product ion patterns of threat agents such as explosives and drugs and some major environmental pollutants (isocyanates and polychlorinated biphenyls (PCBs)) is explored in detail here using PTR-MS, specifically Proton Transfer Reaction Time-of-Flight Mass Spectrometry (PTR-TOF-MS). The proton transfer reaction (PTR) principle works on the detection of the compound in the vapor phase. For some compounds, which have extremely low vapor pressures, both sample and inlet line heating were needed. Generally, the protonated parent molecule (MH+) is found to be the dominant product ion, which therefore provides us with a higher level of confidence in the assignment of a trace compound. However, for several compounds, dissociative proton transfer can occur at various degrees resulting in other product ions. Analysis of other compounds, such as the presence of taggants and impurities were carried out, and in certain compounds unusual E/N anomalies were discovered (E/N is an instrumental set of parameters, where E is the electric field strength and N is the number density). Head space measurements above four different drinks (plain water, tea, red wine and white wine) spiked with four different 'date rape' drugs were also conducted. (author)

  11. Urinary amino acid analysis: a comparison of iTRAQ-LC-MS/MS, GC-MS, and amino acid analyzer.

    Science.gov (United States)

    Kaspar, Hannelore; Dettmer, Katja; Chan, Queenie; Daniels, Scott; Nimkar, Subodh; Daviglus, Martha L; Stamler, Jeremiah; Elliott, Paul; Oefner, Peter J

    2009-07-01

    Urinary amino acid analysis is typically done by cation-exchange chromatography followed by post-column derivatization with ninhydrin and UV detection. This method lacks throughput and specificity. Two recently introduced stable isotope ratio mass spectrometric methods promise to overcome those shortcomings. Using two blinded sets of urine replicates and a certified amino acid standard, we compared the precision and accuracy of gas chromatography/mass spectrometry (GC-MS) and liquid chromatography-tandem mass spectrometry (LC-MS/MS) of propyl chloroformate and iTRAQ derivatized amino acids, respectively, to conventional amino acid analysis. The GC-MS method builds on the direct derivatization of amino acids in diluted urine with propyl chloroformate, GC separation and mass spectrometric quantification of derivatives using stable isotope labeled standards. The LC-MS/MS method requires prior urinary protein precipitation followed by labeling of urinary and standard amino acids with iTRAQ tags containing different cleavable reporter ions distinguishable by MS/MS fragmentation. Means and standard deviations of percent technical error (%TE) computed for 20 amino acids determined by amino acid analyzer, GC-MS, and iTRAQ-LC-MS/MS analyses of 33 duplicate and triplicate urine specimens were 7.27+/-5.22, 21.18+/-10.94, and 18.34+/-14.67, respectively. Corresponding values for 13 amino acids determined in a second batch of 144 urine specimens measured in duplicate or triplicate were 8.39+/-5.35, 6.23+/-3.84, and 35.37+/-29.42. Both GC-MS and iTRAQ-LC-MS/MS are suited for high-throughput amino acid analysis, with the former offering at present higher reproducibility and completely automated sample pretreatment, while the latter covers more amino acids and related amines.

  12. Characterisation of Dissolved Organic Carbon by Thermal Desorption - Proton Transfer Reaction - Mass Spectrometry

    Science.gov (United States)

    Materić, Dušan; Peacock, Mike; Kent, Matthew; Cook, Sarah; Gauci, Vincent; Röckmann, Thomas; Holzinger, Rupert

    2017-04-01

    the samples to the PTR-MS. With thermal desorption lasting just 5 min (at 200˚ C) we successfully detected more than 200 organic ions in the water samples yielding up to 800 ng/mL in total (which corresponds to 1.5% of total DOC present in the sample). Samples were from tropical peatlands in Borneo and Malaysia. Principle component analysis showed a clear separation of the samples when comparing intact and degraded peat swamp forest, and between an oil palm plantation and natural forest. This suggests that the degradation and conversion of tropical peatlands result in distinct changes to DOC composition, with possible implications for associated CO2 emissions. As the method is sensitive and reproducible it has wide potential application in the characterisation of water and of soils. It could provide important information on how land management, microbial activity, vegetation and water treatment control the chemical composition of DOC.

  13. Gas Phase Emission Ratios From In-Use Diesel and CNG Curbside Passenger Buses in New York City

    Science.gov (United States)

    Herndon, S. C.; Shorter, J.; Canagaratna, M.; Jayne, J.; Nelson, D. D.; Wormhoudt, J. C.; Williams, P.; Silva, P. J.; Shi, Q.; Ghertner, A.; Zahniser, M.; Worsnop, D.; Kolb, C.; Lanni, T.; Drewnick, F.; Demerjian, K. L.

    2002-12-01

    The Aerodyne Mobile Laboratory simultaneously measured gas phase and particulate emissions from in use vehicles during two campaigns in New York City. The campaigns took place during two weeks in October, 2000 and four weeks in July-August, 2001. Passenger curbside buses were the primary focus of the study, but school buses and several other heavy duty diesel vehicles were also characterized. This paper describes the methodologies used to measure individual in use vehicles and presents the results of the gas phase measurements. Emission ratios for NO, NO2, SO2, N2O, CO, CH4 and H2CO relative to CO2 have been determined across several classes of buses. The gas phase concentrations were measured each second, using Tunable Infrared Laser Direct Absorption Spectroscopy (TILDAS). Some of the categories of buses into which the data has been sorted are; diesel (both 6V92 and Series 50) with and without the Continuous Regenerative Technology (CRT) retrofit, compressed natural gas powered(CNG) and hybrid diesel-electric buses. The New York Metropolitan Transit Authority (MTA) cooperated with this work, providing details about each of their buses followed. In addition to MTA buses, other New York City passenger bus operators were also measured. In September 2000, MTA began to switch to 30 ppm sulfur diesel fuel while it is believed the non MTA operators did not. The measured emission ratios show that low sulfur fuel greatly reduces the amount of SO2 per CO2. Roughly one third of the MTA fleet of diesel buses have been equipped with the CRT retrofit. The gas phase results of interest in this category show increased direct emission of NO2 and companion work (also submitted to the 12th CRC) show the impact the CRT refit has on particulate emissions. CNG buses show increased H2CO and CH4 emission ratios relative to diesel powered motors.

  14. Atmospheric Benzene Observations from an Oil and Gas Field in the Denver Julesburg Basin in July and August 2014

    Science.gov (United States)

    Halliday, Hannah S.; Thompson, Anne M.; Wisthaler, Armin; Blake, Donald; Hornbrook, Rebecca S.; Mikoviny, Tomas; Mueller, Markus; Eichler, Philipp; Apel, Eric C.; Hills, Alan

    2016-01-01

    High time resolution measurements of volatile organic compounds (VOCs) were collectedusing a proton-transfer-reaction quadrupole mass spectrometry (PTR-QMS) instrument at the PlattevilleAtmospheric Observatory (PAO) in Colorado to investigate how oil and natural gas (ONG) developmentimpacts air quality within the Wattenburg Gas Field (WGF) in the Denver-Julesburg Basin. The measurementswere carried out in July and August 2014 as part of NASAs Deriving Information on Surface Conditions fromColumn and Vertically Resolved Observations Relevant to Air Quality (DISCOVER-AQ) field campaign. ThePTR-QMS data were supported by pressurized whole air canister samples and airborne vertical and horizontalsurveys of VOCs. Unexpectedly high benzene mixing ratios were observed at PAO at ground level (meanbenzene 0.53 ppbv, maximum benzene 29.3 ppbv), primarily at night (mean nighttime benzene 0.73ppbv). These high benzene levels were associated with southwesterly winds. The airborne measurementsindicate that benzene originated from within the WGF, and typical source signatures detected in the canistersamples implicate emissions from ONG activities rather than urban vehicular emissions as primary benzenesource. This conclusion is backed by a regional toluene-to-benzene ratio analysis which associated southerlyflow with vehicular emissions from the Denver area. Weak benzene-to-CO correlations confirmed that trafficemissions were not responsible for the observed high benzene levels. Previous measurements at the BoulderAtmospheric Observatory (BAO) and our data obtained at PAO allow us to locate the source of benzeneenhancements between the two atmospheric observatories. Fugitive emissions of benzene from ONGoperations in the Platteville area are discussed as the most likely causes of enhanced benzene levels at PAO.

  15. Urinary Amino Acid Analysis: A Comparison of iTRAQ®-LC-MS/MS, GC-MS, and Amino Acid Analyzer

    Science.gov (United States)

    Kaspar, Hannelore; Dettmer, Katja; Chan, Queenie; Daniels, Scott; Nimkar, Subodh; Daviglus, Martha L.; Stamler, Jeremiah; Elliott, Paul; Oefner, Peter J.

    2009-01-01

    Urinary amino acid analysis is typically done by cation-exchange chromatography followed by post-column derivatization with ninhydrin and UV detection. This method lacks throughput and specificity. Two recently introduced stable isotope ratio mass spectrometric methods promise to overcome those shortcomings. Using two blinded sets of urine replicates and a certified amino acid standard, we compared the precision and accuracy of gas chromatography/mass spectrometry (GC-MS) and liquid chromatography-tandem mass spectrometry (LC-MS/MS) of propyl chloroformate and iTRAQ® derivatized amino acids, respectively, to conventional amino acid analysis. The GC-MS method builds on the direct derivatization of amino acids in diluted urine with propyl chloroformate, GC separation and mass spectrometric quantification of derivatives using stable isotope labeled standards. The LC-MS/MS method requires prior urinary protein precipitation followed by labeling of urinary and standard amino acids with iTRAQ® tags containing different cleavable reporter ions distinguishable by MS/MS fragmentation. Means and standard deviations of percent technical error (%TE) computed for 20 amino acids determined by amino acid analyzer, GC-MS, and iTRAQ®-LC-MS/MS analyses of 33 duplicate and triplicate urine specimens were 7.27±5.22, 21.18±10.94, and 18.34±14.67, respectively. Corresponding values for 13 amino acids determined in a second batch of 144 urine specimens measured in duplicate or triplicate were 8.39±5.35, 6.23±3.84, and 35.37±29.42. Both GC-MS and iTRAQ®-LC-MS/MS are suited for high-throughput amino acid analysis, with the former offering at present higher reproducibility and completely automated sample pretreatment, while the latter covers more amino acids and related amines. PMID:19481989

  16. POLYCYCLIC AROMATIC HYDROCARBON AND EMISSION LINE RATIOS IN ACTIVE GALACTIC NUCLEI AND STARBURST GALAXIES

    International Nuclear Information System (INIS)

    Sales, Dinalva A.; Pastoriza, M. G.; Riffel, R.

    2010-01-01

    We study the polycyclic aromatic hydrocarbon (PAH) bands, ionic emission lines, and mid-infrared continuum properties in a sample of 171 emission line galaxies taken from the literature plus 15 new active galactic nucleus (AGN) Spitzer spectra. We normalize the spectra at λ = 23 μm and grouped them according to the type of nuclear activity. The continuum shape steeply rises for longer wavelengths and can be fitted with a warm blackbody distribution of T ∼ 150-300 K. The brightest PAH spectral bands (6.2, 7.7, 8.6, 11.3, and 12.7 μm) and the forbidden emission lines of [Si II] 34.8 μm, [Ar II] 6.9 μm, [S III] 18.7 and 33.4 μm were detected in all the starbursts and in ∼80% of the Seyfert 2. Taking under consideration only the PAH bands at 7.7 μm, 11.3 μm, and 12.7 μm, we find that they are present in ∼80% of the Seyfert 1, while only half of this type of activity show the 6.2 μm and 8.6 μm PAH bands. The observed intensity ratios for neutral and ionized PAHs (6.2 μm/7.7 μm x 11.3 μm/7.7 μm) were compared to theoretical intensity ratios, showing that AGNs have higher ionization fraction and larger PAH molecules (≥180 carbon atoms) than SB galaxies. The ratio between the ionized (7.7 μm) and the neutral PAH bands (8.6 μm and 11.3 μm) are distributed over different ranges for AGNs and SB galaxies, suggesting that these ratios could depend on the ionization fraction, as well as on the hardness of the radiation field. The ratio between the 7.7 μm and 11.3 μm bands is nearly constant with the increase of [Ne III]15.5 μm/[Ne II] 12.8 μm, indicating that the fraction of ionized to neutral PAH bands does not depend on the hardness of the radiation field. The equivalent width of both PAH features show the same dependence (strongly decreasing) with [Ne III]/[Ne II], suggesting that the PAH molecules, emitting either ionized (7.7 μm) or neutral (11.3 μm) bands, may be destroyed with the increase of the hardness of the radiation field.

  17. Benzene observations and source appointment in a region of oil and natural gas development

    Science.gov (United States)

    Halliday, Hannah Selene

    Benzene is a primarily anthropogenic volatile organic compound (VOC) with a small number of well characterized sources. Atmospheric benzene affects human health and welfare, and low level exposure (Atmospheric Observatory (PAO) in Colorado to investigate how O&NG development impacts air quality within the Wattenburg Gas Field (WGF) in the Denver-Julesburg Basin. The measurements were carried out in July and August 2014 as part of NASA's DISCOVER-AQ field campaign. The PTR-QMS data were supported by pressurized whole air canister samples and airborne vertical and horizontal surveys of VOCs. Unexpectedly high benzene mixing ratios were observed at PAO at ground level (mean benzene = 0.53 ppbv, maximum benzene = 29.3 ppbv), primarily at night (mean nighttime benzene = 0.73 ppbv). These high benzene levels were associated with southwesterly winds. The airborne measurements indicate that benzene originated from within the WGF, and typical source signatures detected in the canister samples implicate emissions from O&NG activities rather than urban vehicular emissions as primary benzene source. This conclusion is backed by a regional toluene-to-benzene ratio analysis which associated southerly flow with vehicular emissions from the Denver area. Weak benzene-to-CO correlations confirmed that traffic emissions were not responsible for the observed high benzene levels. Previous measurements at the Boulder Atmospheric Observatory (BAO) and our data obtained at PAO allow us to locate the source of benzene enhancements between the two atmospheric observatories. Fugitive emissions of benzene from O&NG operations in the Platteville area are discussed as the most likely causes of enhanced benzene levels at PAO. A limited information source attribution with the PAO dataset was completed using the EPA's positive matrix factorization (PMF) source receptor model. Six VOCs from the PTR-QMS measurement were used along with CO and NO for a total of eight chemical species. Six sources

  18. Atmospheric benzene observations from oil and gas production in the Denver-Julesburg Basin in July and August 2014

    Science.gov (United States)

    Halliday, Hannah S.; Thompson, Anne M.; Wisthaler, Armin; Blake, Donald R.; Hornbrook, Rebecca S.; Mikoviny, Tomas; Müller, Markus; Eichler, Philipp; Apel, Eric C.; Hills, Alan J.

    2016-09-01

    High time resolution measurements of volatile organic compounds (VOCs) were collected using a proton-transfer-reaction quadrupole mass spectrometry (PTR-QMS) instrument at the Platteville Atmospheric Observatory (PAO) in Colorado to investigate how oil and natural gas (O&NG) development impacts air quality within the Wattenburg Gas Field (WGF) in the Denver-Julesburg Basin. The measurements were carried out in July and August 2014 as part of NASA's "Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality" (DISCOVER-AQ) field campaign. The PTR-QMS data were supported by pressurized whole air canister samples and airborne vertical and horizontal surveys of VOCs. Unexpectedly high benzene mixing ratios were observed at PAO at ground level (mean benzene = 0.53 ppbv, maximum benzene = 29.3 ppbv), primarily at night (mean nighttime benzene = 0.73 ppbv). These high benzene levels were associated with southwesterly winds. The airborne measurements indicate that benzene originated from within the WGF, and typical source signatures detected in the canister samples implicate emissions from O&NG activities rather than urban vehicular emissions as primary benzene source. This conclusion is backed by a regional toluene-to-benzene ratio analysis which associated southerly flow with vehicular emissions from the Denver area. Weak benzene-to-CO correlations confirmed that traffic emissions were not responsible for the observed high benzene levels. Previous measurements at the Boulder Atmospheric Observatory (BAO) and our data obtained at PAO allow us to locate the source of benzene enhancements between the two atmospheric observatories. Fugitive emissions of benzene from O&NG operations in the Platteville area are discussed as the most likely causes of enhanced benzene levels at PAO.

  19. Emission Ratios for Ammonia and Formic Acid and Observations of Peroxy Acetyl Nitrate (PAN and Ethylene in Biomass Burning Smoke as Seen by the Tropospheric Emission Spectrometer (TES

    Directory of Open Access Journals (Sweden)

    Vivienne H. Payne

    2011-11-01

    Full Text Available We use the Tropospheric Emission Spectrometer (TES aboard the NASA Aura satellite to determine the concentrations of the trace gases ammonia (NH3 and formic acid (HCOOH within boreal biomass burning plumes, and present the first detection of peroxy acetyl nitrate (PAN and ethylene (C2H4 by TES. We focus on two fresh Canadian plumes observed by TES in the summer of 2008 as part of the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS-B campaign. We use TES retrievals of NH3 and HCOOH within the smoke plumes to calculate their emission ratios (1.0% ± 0.5% and 0.31% ± 0.21%, respectively relative to CO for these Canadian fires. The TES derived emission ratios for these gases agree well with previous aircraft and satellite estimates, and can complement ground-based studies that have greater surface sensitivity. We find that TES observes PAN mixing ratios of ~2 ppb within these mid-tropospheric boreal biomass burning plumes when the average cloud optical depth is low ( < 0.1 and that TES can detect C2H4 mixing ratios of ~2 ppb in fresh biomass burning smoke plumes.

  20. Carbon dioxide emissions and the overshoot ratio change resulting from the implementation of 2nd Energy Master Plan in South Korea

    Science.gov (United States)

    Yeo, M. J.; Kim, Y. P.

    2015-12-01

    The direction of the energy policies of the country is important in the projection of environmental impacts of the country. The greenhouse gases (GHGs) emission of the energy sector in South Korea is very huge, about 600 MtCO2e in 2011. Also the carbon footprint due to the energy consumption contributes to the ecological footprint is also large, more than 60%. Based on the official plans (the national greenhouse gases emission reduction target for 2030 (GHG target for 2030) and the 2nd Energy Master Plan (2nd EMP)), several scenarios were proposed and the sensitivity of the GHG emission amount and 'overshoot ratio' which is the ratio of ecological footprint to biocapacity were estimated. It was found that to meet the GHG target for 2030 the ratio of non-emission energy for power generation should be over 71% which would be very difficult. We also found that the overshoot ratio would increase from 5.9 in 2009 to 7.6 in 2035. Thus, additional efforts are required to reduce the environmental burdens in addition to optimize the power mix configuration. One example is the conversion efficiency in power generation. If the conversion efficiency in power generation rises up 50% from the current level, 40%, the energy demand and resultant carbon dioxide emissions would decrease about 10%. Also the influence on the environment through changes in consumption behavior, for example, the diet choice is expected to be meaningful.

  1. A dual tracer ratio method for comparative emission measurements in an experimental dairy housing

    Science.gov (United States)

    Mohn, Joachim; Zeyer, Kerstin; Keck, Margret; Keller, Markus; Zähner, Michael; Poteko, Jernej; Emmenegger, Lukas; Schrade, Sabine

    2018-04-01

    Agriculture, and in particular dairy farming, is an important source of ammonia (NH3) and non-carbon dioxide greenhouse gas (GHG) emissions. This calls for the development and quantification of effective mitigation strategies. Our study presents the implementation of a dual tracer ratio method in a novel experimental dairy housing with two identical, but spatially separated housing areas. Modular design and flexible floor elements allow the assessment of structural, process engineering and organisational abatement measures at practical scale. Thereby, the emission reduction potential of specific abatement measures can be quantified in relation to a reference system. Emissions in the naturally ventilated housing are determined by continuous dosing of two artificial tracers (sulphur hexafluoride SF6, trifluoromethylsulphur pentafluoride SF5CF3) and their real-time detection in the ppt range with an optimized GC-ECD method. The two tracers are dosed into different experimental sections, which enables the independent assessment of both housing areas. Mass flow emissions of NH3 and GHGs are quantified by areal dosing of tracer gases and multipoint sampling as well as real-time analysis of both tracer and target gases. Validation experiments demonstrate that the technique is suitable for both areal and point emission sources and achieves an uncertainty of less than 10% for the mass emissions of NH3, methane (CH4) and carbon dioxide (CO2), which is superior to other currently available methods. Comparative emission measurements in this experimental dairy housing will provide reliable, currently unavailable information on emissions for Swiss dairy farming and demonstrate the reduction potential of mitigation measures for NH3, GHGs and potentially other pollutants.

  2. Performance analysis of passive time reversal communication technique for multipath interference in shallow sea acoustic channel

    Science.gov (United States)

    Kida, Yukihiro; Shimura, Takuya; Deguchi, Mitsuyasu; Watanabe, Yoshitaka; Ochi, Hiroshi; Meguro, Koji

    2017-07-01

    In this study, the performance of passive time reversal (PTR) communication techniques in multipath rich underwater acoustic environments is investigated. It is recognized empirically and qualitatively that a large number of multipath arrivals could generally raise the demodulation result of PTR. However, the relationship between multipath and the demodulation result is hardly evaluated quantitatively. In this study, the efficiency of the PTR acoustic communication techniques for multipath interference cancelation was investigated quantitatively by applying a PTR-DFE (decision feed-back filter) scheme to a synthetic dataset of a horizontal underwater acoustic channel. Mainly, in this study, we focused on the relationship between the signal-to-interference ratio (SIR) of datasets and the output signal-to-noise ratio (OSNR) of demodulation results by a parametric study approach. As a result, a proportional relation between SIR and OSNR is confirmed in low-SNR datasets. It was also found that PTR has a performance limitation, that is OSNR converges to a typical value depending on the number of receivers. In conclusion, results indicate that PTR could utilize the multipath efficiently and also withstand the negative effects of multipath interference at a given limitation.

  3. Characterisation of the volatile profiles of infant formulas by proton transfer reaction-mass spectrometry and gas chromatography-mass spectrometry

    NARCIS (Netherlands)

    Ruth, van S.M.; Floris, V.; Fayoux, S.

    2006-01-01

    The volatile profiles of 13 infant formulas were evaluated by proton transfer reaction-mass spectrometry (PTR-MS) and gas chromatography¿mass spectrometry (GC¿MS). The infant formulas varied in brand (Aptamil, Cow & Gate, SMA), type (for different infant target groups) and physical form

  4. Defect controlled tuning of the ratio of ultraviolet to visible light emission in TiO2 thin films

    International Nuclear Information System (INIS)

    Mondal, S.; Basak, D.

    2016-01-01

    The photoluminescence (PL) of sol–gel TiO 2 thin film has been found to be largely dependent on the post-deposition processing such as annealing at 500 °C in air, vacuum and ultraviolet (UV) light curing at room temperature. A detailed analysis of room temperature PL spectra shows that the UV/VIS PL peak intensity ratio is maximum for the film which has been annealed at 500 °C in air. X-ray photoelectron spectroscopy confirms the presence of Ti 3+ type of point defects. The visible emission is deconvoluted to green and orange emissions. Analyses of the present experimental results indicate that V O and/or Ti 3+ causes the green emission and OH and/or excess O 2 adsorption on TiO 2 surface probably causes the orange emission. The time correlated single photon counting spectroscopy data of the UV PL indicates higher number defects in vacuum annealed and UV cured films as compared to the air annealed film. Correlation of the results altogether allows us to conclude that the surface defects those causing the visible emission are smaller in number in the air annealed film. The present results may be useful for tuning the relative PL intensities of UV, green and orange emissions. - Highlights: • Sol–gel TiO 2 films were treated both in air, vacuum at 500 °C and under UV light (room temperature). • UV/VIS PL intensity ratio is maximum for air annealed and minimum for UV cured films. • Both green and orange emission predominantly controls the visible emission of TiO 2 . • The visible emission exhibit a clear correlation with Ti 3+  defects on the surface.

  5. Genuineness assessment of mandarin essential oils employing gas chromatography-combustion-isotope ratio MS (GC-C-IRMS).

    Science.gov (United States)

    Schipilliti, Luisa; Tranchida, Peter Quinto; Sciarrone, Danilo; Russo, Marina; Dugo, Paola; Dugo, Giovanni; Mondello, Luigi

    2010-03-01

    Cold-pressed mandarin essential oils are products of great economic importance in many parts of the world and are used in perfumery, as well as in food products. Reconstituted mandarin oils are easy to find on the market; useful information on essential oil authenticity, quality, extraction technique, geographic origin and biogenesis can be attained through high-resolution GC of the volatile fraction, or enantioselective GC, using different chiral stationary phases. Stable isotope ratio analysis has gained considerable interest for the unveiling of citrus oil adulteration, detecting small differences in the isotopic carbon composition and providing plenty of information concerning the discrimination among products of different geographical origin and the adulteration of natural essential oils with synthetic or natural compounds. In the present research, the authenticity of several mandarin essential oils was assessed through the employment of GC hyphenated to isotope ratio MS, conventional GC flame ionization detector, enantioselective GC and HPLC. Commercial mandarin oils and industrial natural (declared as such) mandarin essential oils, characterized by different harvest periods and geographic origins, were subjected to analysis. The results attained were compared with those of genuine cold-pressed Italian mandarin oils, obtained during the 2008-2009 harvest season.

  6. From 'Roentgen' to 'effective dose'. Cooperation of PTR/PTB with Standard Committee Radiology in the development of radiation protection dosimetry

    International Nuclear Information System (INIS)

    Alberts, W.G.; Dietze, G.; Hohlfeld, K.

    1995-01-01

    The development of quantities and units in the field of radiation protection dosimetry is demonstrated by some examples. This development is strongly connected with work performed at the PTR/PTB and the work of the ''Normenausschuss Radiologie (NAR) im DIN''. In the following the new radiation protection operational quantities are described which have been recommended by the international commissions ICRU and ICRP for use in area and individual monitoring of external radiation. It is aimed to introduce these quantities in Germany in 1995 - also in legal metrology. (orig.) [de

  7. Development of net energy ratio and emission factor for quad-generation pathways

    DEFF Research Database (Denmark)

    Rudra, Souman; Rosendahl, Lasse; Kumar, Amit

    2014-01-01

    of this study was to evaluate the energy performance, reduce GHG and acid rain precursor emission, and use of biomass for different outputs based on demand. Finally, a sensitivity analysis and a comparative study ar conducted for expected technological improvements and factors that could increase the energy......, methanol and methane. Circulating fluidized bed gasifier and the gas technology institute (GTI) gasifier technologies are used for this quad-generation process. Two different biomass feedstocks are considered in this study. The net energy ratio for six different pathways having the range of between 1...

  8. Enhanced Isotopic Ratio Outlier Analysis (IROA Peak Detection and Identification with Ultra-High Resolution GC-Orbitrap/MS: Potential Application for Investigation of Model Organism Metabolomes

    Directory of Open Access Journals (Sweden)

    Yunping Qiu

    2018-01-01

    Full Text Available Identifying non-annotated peaks may have a significant impact on the understanding of biological systems. In silico methodologies have focused on ESI LC/MS/MS for identifying non-annotated MS peaks. In this study, we employed in silico methodology to develop an Isotopic Ratio Outlier Analysis (IROA workflow using enhanced mass spectrometric data acquired with the ultra-high resolution GC-Orbitrap/MS to determine the identity of non-annotated metabolites. The higher resolution of the GC-Orbitrap/MS, together with its wide dynamic range, resulted in more IROA peak pairs detected, and increased reliability of chemical formulae generation (CFG. IROA uses two different 13C-enriched carbon sources (randomized 95% 12C and 95% 13C to produce mirror image isotopologue pairs, whose mass difference reveals the carbon chain length (n, which aids in the identification of endogenous metabolites. Accurate m/z, n, and derivatization information are obtained from our GC/MS workflow for unknown metabolite identification, and aids in silico methodologies for identifying isomeric and non-annotated metabolites. We were able to mine more mass spectral information using the same Saccharomyces cerevisiae growth protocol (Qiu et al. Anal. Chem 2016 with the ultra-high resolution GC-Orbitrap/MS, using 10% ammonia in methane as the CI reagent gas. We identified 244 IROA peaks pairs, which significantly increased IROA detection capability compared with our previous report (126 IROA peak pairs using a GC-TOF/MS machine. For 55 selected metabolites identified from matched IROA CI and EI spectra, using the GC-Orbitrap/MS vs. GC-TOF/MS, the average mass deviation for GC-Orbitrap/MS was 1.48 ppm, however, the average mass deviation was 32.2 ppm for the GC-TOF/MS machine. In summary, the higher resolution and wider dynamic range of the GC-Orbitrap/MS enabled more accurate CFG, and the coupling of accurate mass GC/MS IROA methodology with in silico fragmentation has great

  9. Enhanced Isotopic Ratio Outlier Analysis (IROA) Peak Detection and Identification with Ultra-High Resolution GC-Orbitrap/MS: Potential Application for Investigation of Model Organism Metabolomes.

    Science.gov (United States)

    Qiu, Yunping; Moir, Robyn D; Willis, Ian M; Seethapathy, Suresh; Biniakewitz, Robert C; Kurland, Irwin J

    2018-01-18

    Identifying non-annotated peaks may have a significant impact on the understanding of biological systems. In silico methodologies have focused on ESI LC/MS/MS for identifying non-annotated MS peaks. In this study, we employed in silico methodology to develop an Isotopic Ratio Outlier Analysis (IROA) workflow using enhanced mass spectrometric data acquired with the ultra-high resolution GC-Orbitrap/MS to determine the identity of non-annotated metabolites. The higher resolution of the GC-Orbitrap/MS, together with its wide dynamic range, resulted in more IROA peak pairs detected, and increased reliability of chemical formulae generation (CFG). IROA uses two different 13 C-enriched carbon sources (randomized 95% 12 C and 95% 13 C) to produce mirror image isotopologue pairs, whose mass difference reveals the carbon chain length (n), which aids in the identification of endogenous metabolites. Accurate m/z, n, and derivatization information are obtained from our GC/MS workflow for unknown metabolite identification, and aids in silico methodologies for identifying isomeric and non-annotated metabolites. We were able to mine more mass spectral information using the same Saccharomyces cerevisiae growth protocol (Qiu et al. Anal. Chem 2016) with the ultra-high resolution GC-Orbitrap/MS, using 10% ammonia in methane as the CI reagent gas. We identified 244 IROA peaks pairs, which significantly increased IROA detection capability compared with our previous report (126 IROA peak pairs using a GC-TOF/MS machine). For 55 selected metabolites identified from matched IROA CI and EI spectra, using the GC-Orbitrap/MS vs. GC-TOF/MS, the average mass deviation for GC-Orbitrap/MS was 1.48 ppm, however, the average mass deviation was 32.2 ppm for the GC-TOF/MS machine. In summary, the higher resolution and wider dynamic range of the GC-Orbitrap/MS enabled more accurate CFG, and the coupling of accurate mass GC/MS IROA methodology with in silico fragmentation has great potential in

  10. The use of ICP-MS and LA-ICP-MS techniques for uranium analysis in real-life swipe samples for safeguards purposes

    Energy Technology Data Exchange (ETDEWEB)

    Pestana, Rafael C.B.; Sarkis, Jorge E.S.; Carvalho, Elita F.U., E-mail: rcbpestana@gmail.com, E-mail: jesarkis@ipen.br [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil); Abreu Junior, Cassio H. [Centro de Energia Nuclear na Agricultura (CENA/USP), Piracicaba, SP (Brazil)

    2013-07-01

    Environmental swipe sampling for safeguards purposes is a powerful tool to detect undeclared materials and activities, and has been used by the International Atomic Energy Agency since 1997. This work describes the utilization of the inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) for determining uranium isotopic ratios in a real-life swipe samples collected in a conversion plant at IPEN/CNEN, Brazil. Uncertainties were estimated by following the International Organization for Standardization - Guide to the Expression of Uncertainties in Measurement (ISO GUM), with a confidence level of 95%. The major uncertainties percentage for n({sup 235}U)/n({sup 238}U) ratio for ICP-MS was 3% and for LA-ICP-MS was 30% The values of uranium isotopic ratios obtained for each technique demonstrate the viability of these analytical techniques as an alternative tool for uranium analysis in swipe samples for safeguards purposes. (author)

  11. The use of ICP-MS and LA-ICP-MS techniques for uranium analysis in real-life swipe samples for safeguards purposes

    International Nuclear Information System (INIS)

    Pestana, Rafael C.B.; Sarkis, Jorge E.S.; Carvalho, Elita F.U.; Abreu Junior, Cassio H.

    2013-01-01

    Environmental swipe sampling for safeguards purposes is a powerful tool to detect undeclared materials and activities, and has been used by the International Atomic Energy Agency since 1997. This work describes the utilization of the inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) for determining uranium isotopic ratios in a real-life swipe samples collected in a conversion plant at IPEN/CNEN, Brazil. Uncertainties were estimated by following the International Organization for Standardization - Guide to the Expression of Uncertainties in Measurement (ISO GUM), with a confidence level of 95%. The major uncertainties percentage for n( 235 U)/n( 238 U) ratio for ICP-MS was 3% and for LA-ICP-MS was 30% The values of uranium isotopic ratios obtained for each technique demonstrate the viability of these analytical techniques as an alternative tool for uranium analysis in swipe samples for safeguards purposes. (author)

  12. Effect of compression ratio on performance, combustion and emission characteristics of a dual fuel diesel engine run on raw biogas

    International Nuclear Information System (INIS)

    Bora, Bhaskor J.; Saha, Ujjwal K.; Chatterjee, Soumya; Veer, Vijay

    2014-01-01

    Highlights: • Maximum brake thermal efficiency of 20.04% was obtained in dual fuel mode. • Compression ratio of 18 produced the maximum brake thermal efficiency. • Maximum replacement of diesel was found to be 79.46% at a compression ratio of 18. • CO gets reduced by 26.22% with the increase of compression ratio from 16 to18. • HC gets reduced by 41.97% with the increase of compression ratio from 16 to18. - Abstract: The energy consumption of the world is increasing at a staggering rate due to population explosion. The extensive use of energy has led to fossil fuel depletion and the rise in pollution. Renewable energy holds the key solution to these aforementioned problems. Biogas, one such renewable fuel, can be used in a diesel engine under dual fuel mode for the generation of power. This work attempts to unfold the effect of compression ratio on the performance, combustion and emission characteristics of a dual fuel diesel engine run on raw biogas. For this investigation, a 3.5 kW single cylinder, direct injection, water cooled, variable compression ratio diesel engine is converted into a biogas run dual fuel diesel engine by connecting a venturi gas mixer at the inlet manifold. Experiments have been conducted at various compression ratios (18, 17.5, 17 and 16) and under different loading conditions fixing the standard injection timing at 23° before top dead centre. At 100% load, the brake thermal efficiencies of the dual fuel mode are found to be 20.04%, 18.25%, 17.07% and 16.42% at compression ratios of 18, 17.5, 17 and 16, respectively, whereas at the same load, the diesel mode shows an efficiency of 27.76% at a compression ratio of 17.5. The maximum replacement of the precious fossil fuel is found to be 79.46%, 76.1%, 74% and 72% at compression ratios of 18, 17.5, 17 and 16, respectively at 100% load. For the dual fuel mode, on an average, there is a reduction in carbon monoxide as well as hydrocarbon emission by 26.22% and 41.97% when compression

  13. Selected Ion Flow-Drift Tube Mass Spectrometry: Quantification of Volatile Compounds in Air and Breath

    Czech Academy of Sciences Publication Activity Database

    Spesyvyi, Anatolii; Smith, D.; Španěl, Patrik

    2015-01-01

    Roč. 87, č. 24 (2015), s. 12151-12160 ISSN 0003-2700 R&D Projects: GA ČR GA13-28882S Institutional support: RVO:61388955 Keywords : TRACE GAS-ANALYSIS * SIFT-MS * PTR-MS Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.886, year: 2015

  14. Galaxy emission line classification using three-dimensional line ratio diagrams

    Energy Technology Data Exchange (ETDEWEB)

    Vogt, Frédéric P. A.; Dopita, Michael A.; Kewley, Lisa J.; Sutherland, Ralph S. [Research School of Astronomy and Astrophysics, Australian National University, Canberra, ACT 2611 (Australia); Scharwächter, Julia [Observatoire de Paris, LERMA (CNRS: UMR8112), 61 Av. de l' Observatoire, F-75014 Paris (France); Basurah, Hassan M.; Ali, Alaa; Amer, Morsi A., E-mail: frederic.vogt@anu.edu.au [Astronomy Department, King Abdulaziz University, P.O. Box 80203, Jeddah (Saudi Arabia)

    2014-10-01

    Two-dimensional (2D) line ratio diagnostic diagrams have become a key tool in understanding the excitation mechanisms of galaxies. The curves used to separate the different regions—H II-like or excited by an active galactic nucleus (AGN)—have been refined over time but the core technique has not evolved significantly. However, the classification of galaxies based on their emission line ratios really is a multi-dimensional problem. Here we exploit recent software developments to explore the potential of three-dimensional (3D) line ratio diagnostic diagrams. We introduce the ZQE diagrams, which are a specific set of 3D diagrams that separate the oxygen abundance and the ionization parameter of H II region-like spectra and also enable us to probe the excitation mechanism of the gas. By examining these new 3D spaces interactively, we define the ZE diagnostics, a new set of 2D diagnostics that can provide the metallicity of objects excited by hot young stars and that cleanly separate H II region-like objects from the different classes of AGNs. We show that these ZE diagnostics are consistent with the key log [N II]/Hα versus log [O III]/Hβ diagnostic currently used by the community. They also have the advantage of attaching a probability that a given object belongs to one class or the other. Finally, we discuss briefly why ZQE diagrams can provide a new way to differentiate and study the different classes of AGNs in anticipation of a dedicated follow-up study.

  15. Application of ICP-MS and AMS for determination of Pu- and U-isotope ratios for source identification

    Energy Technology Data Exchange (ETDEWEB)

    Skipperud, L. (Norwegian Univ. of Life Sciences, Isotope Lab.. Dept. of Plant and Environmental Sciences, AAs (Norway))

    2010-03-15

    the Pu-240/Pu-239 ratio offers a reliable way of distinguishing weapon's grade sources from global fallout. Since these two isotopes are not separated easily by conventional alfa spectrometry techniques, mass spectrometry is required for an assessment of the isotope ratios. Because of the low levels of plutonium in the Arctic area, plutonium concentrations and 240/239 ratios have been determined using accelerator mass spectrometry (AMS), which has proved a useful and reliable method for analysis of plutonium. ICP-MS has proven to be a good tool together with traditional alfa spectrometry when it comes to analysing plutonium and its isotope ratios in more contaminated areas. (author)

  16. Improvements in Precise and Accurate Isotope Ratio Determination via LA-MC-ICP-MS by Application of an Alternative Data Reduction Protocol

    Science.gov (United States)

    Fietzke, J.; Liebetrau, V.; Guenther, D.; Frische, M.; Zumholz, K.; Hansteen, T. H.; Eisenhauer, A.

    2008-12-01

    An alternative approach for the evaluation of isotope ratio data using LA-MC-ICP-MS will be presented. In contrast to previously applied methods it is based on the simultaneous responses of all analyte isotopes of interest and the relevant interferences without performing a conventional background correction. Significant improvements in precision and accuracy can be achieved when applying this new method and will be discussed based on the results of two first methodical applications: a) radiogenic and stable Sr isotopes in carbonates b) stable chlorine isotopes of pyrohydrolytic extracts. In carbonates an external reproducibility of the 87Sr/86Sr ratios of about 19 ppm (RSD) was achieved, an improvement of about a factor of 5. For recent and sub-recent marine carbonates a mean radiogenic strontium isotope ratio 87Sr/86Sr of 0.709170±0.000007 (2SE) was determined, which agrees well with the value of 0.7091741±0.0000024 (2SE) reported for modern sea water [1,2]. Stable chlorine isotope ratios were determined ablating pyrohydrolytic extracts with a reproducibility of about 0.05‰ (RSD). For basaltic reference material JB1a and JB2 chlorine isotope ratios were determined relative to SMOC (standard mean ocean chlorinity) δ37ClJB-1a = (-0.99±0.06) ‰ and δ37ClJB-1a = (-0.60±0.03) ‰ (SD), respectively, in accordance with published data [3]. The described strategies for data reduction are considered to be generally applicable for all isotope ratio measurements using LA-MC-ICP-MS. [1] J.M. McArthur, D. Rio, F. Massari, D. Castradori, T.R. Bailey, M. Thirlwall, S. Houghton, Palaeogeo. Palaeoclim. Palaeoeco., 2006, 242 (126), doi: 10.1016/j.palaeo.2006.06.004 [2] J. Fietzke, V. Liebetrau, D. Guenther, K. Guers, K. Hametner, K. Zumholz, T.H. Hansteen and A. Eisenhauer, J. Anal. At. Spectrom., 2008, 23, 955-961, doi:10.1039/B717706B [3] J. Fietzke, M. Frische, T.H. Hansteen and A. Eisenhauer, J. Anal. At. Spectrom., 2008, 23, 769-772, doi:10.1039/B718597A

  17. Sensitivity of GC-EI/MS, GC-EI/MS/MS, LC-ESI/MS/MS, LC-Ag(+) CIS/MS/MS, and GC-ESI/MS/MS for analysis of anabolic steroids in doping control.

    Science.gov (United States)

    Cha, Eunju; Kim, Sohee; Kim, Ho Jun; Lee, Kang Mi; Kim, Ki Hun; Kwon, Oh-Seung; Lee, Jaeick

    2015-01-01

    This study compared the sensitivity of various separation and ionization methods, including gas chromatography with an electron ionization source (GC-EI), liquid chromatography with an electrospray ionization source (LC-ESI), and liquid chromatography with a silver ion coordination ion spray source (LC-Ag(+) CIS), coupled to a mass spectrometer (MS) for steroid analysis. Chromatographic conditions, mass spectrometric transitions, and ion source parameters were optimized. The majority of steroids in GC-EI/MS/MS and LC-Ag(+) CIS/MS/MS analysis showed higher sensitivities than those obtained with other analytical methods. The limits of detection (LODs) of 65 steroids by GC-EI/MS/MS, 68 steroids by LC-Ag(+) CIS/MS/MS, 56 steroids by GC-EI/MS, 54 steroids by LC-ESI/MS/MS, and 27 steroids by GC-ESI/MS/MS were below cut-off value of 2.0 ng/mL. LODs of steroids that formed protonated ions in LC-ESI/MS/MS analysis were all lower than the cut-off value. Several steroids such as unconjugated C3-hydroxyl with C17-hydroxyl structure showed higher sensitivities in GC-EI/MS/MS analysis relative to those obtained using the LC-based methods. The steroids containing 4, 9, 11-triene structures showed relatively poor sensitivities in GC-EI/MS and GC-ESI/MS/MS analysis. The results of this study provide information that may be useful for selecting suitable analytical methods for confirmatory analysis of steroids. Copyright © 2015 John Wiley & Sons, Ltd.

  18. The Atmospheric Chemistry of Methyl Chavicol (Estragole)

    Science.gov (United States)

    Bloss, W. J.; Alam, M. S.; Rickard, A. R.; Hamilton, J. F.; Pereira, K. F.; Camredon, M.; Munoz, A.; Vazquez, M.; Alacreu, P.; Rodenas, M.; Vera, T.

    2012-12-01

    The oxidation of volatile organic compounds (VOCs) leads to formation of ozone and secondary organic aerosols (SOA), with consequences for health, air quality, crop yields, atmospheric chemistry and radiative transfer. It is estimated that ca. 90 % of VOC emissions to the atmosphere originate from biogenic sources (BVOC); such emissions may increase under future climates. Recent field observations have identified Methyl Chavicol ("MC" hereafter, also known as Estragole; 1-allyl-4-methoxybenzene, C10H12O) as a major BVOC above pine forests in the USA [Bouvier-Brown et al., 2009], and within an oil palm plantation in Malaysian Borneo, where it was found that MC could represent the highest single floral contribution of reactive carbon to the atmosphere [Misztal et al., 2010]. Palm oil cultivation, and hence emissions of MC, may be expected to increase with societal food and biofuel demand. We present the results of a series of simulation chamber experiments to assess the atmospheric fate of MC. Experiments were performed in the EUPHORE (European Photoreactor) facility in Valencia, Spain (200 m3 outdoor smog chamber), investigating the degradation of MC by reaction with OH, O3 and NO3. An extensive range of measurement instrumentation was used to monitor precursor and product formation, including stable species (FTIR, PTR-MS, GC-FID and GC-MS), radical intermediates (LIF), inorganic components (NOx, O3, HONO (LOPAP and aerosol production (SMPS) and composition (PILS and filters; analysed offline by LC-MS and FTICR-MS). Experiments were conducted at a range of NOx:VOC ratios, and in the presence and absence of radical (OH) scavenger compounds. This chamber dataset is used to determine the rate constants for reaction of MC with OH, O3 and NO3, the ozonolysis radical yields, and identify the primary degradation products for each initiation route, alongside the aerosol mass yields. Aerosol composition measurements are analysed to identify markers for MC contributions to

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

    Science.gov (United States)

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

    2015-09-02

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

  20. Combining tracer flux ratio methodology with low-flying aircraft measurements to estimate dairy farm CH4 emissions

    Science.gov (United States)

    Daube, C.; Conley, S.; Faloona, I. C.; Yacovitch, T. I.; Roscioli, J. R.; Morris, M.; Curry, J.; Arndt, C.; Herndon, S. C.

    2017-12-01

    Livestock activity, enteric fermentation of feed and anaerobic digestion of waste, contributes significantly to the methane budget of the United States (EPA, 2016). Studies question the reported magnitude of these methane sources (Miller et. al., 2013), calling for more detailed research of agricultural animals (Hristov, 2014). Tracer flux ratio is an attractive experimental method to bring to this problem because it does not rely on estimates of atmospheric dispersion. Collection of data occurred during one week at two dairy farms in central California (June, 2016). Each farm varied in size, layout, head count, and general operation. The tracer flux ratio method involves releasing ethane on-site with a known flow rate to serve as a tracer gas. Downwind mixed enhancements in ethane (from the tracer) and methane (from the dairy) were measured, and their ratio used to infer the unknown methane emission rate from the farm. An instrumented van drove transects downwind of each farm on public roads while tracer gases were released on-site, employing the tracer flux ratio methodology to assess simultaneous methane and tracer gas plumes. Flying circles around each farm, a small instrumented aircraft made measurements to perform a mass balance evaluation of methane gas. In the course of these two different methane quantification techniques, we were able to validate yet a third method: tracer flux ratio measured via aircraft. Ground-based tracer release rates were applied to the aircraft-observed methane-to-ethane ratios, yielding whole-site methane emission rates. Never before has the tracer flux ratio method been executed with aircraft measurements. Estimates from this new application closely resemble results from the standard ground-based technique to within their respective uncertainties. Incorporating this new dimension to the tracer flux ratio methodology provides additional context for local plume dynamics and validation of both ground and flight-based data.

  1. Quantifying impacts on air quality of vehicular emissions in Sao Paulo and Rio de Janeiro

    Science.gov (United States)

    Artaxo, Paulo; Ferreira de Brito, Joel; Godoy, José Marcus; Luiza Godoy, Maria; Junior, Djacinto

    2016-04-01

    Vehicular emissions in megacities such as Sao Paulo and Rio de Janeiro are increasingly becoming a global issue. The São Paulo Metropolitan Area (SPMA), located in Southeast of Brazil, is a megacity with a population of 18 million people, with 7 million cars and large-scale industrial emissions. Rio de Janeiro is also a large city with different meteorology than São Paulo. All cars in Brazil runs gasohol, with 23% ethanol in gasoline, and for the last 10 years, flex cars that can run on gasohol, ethanol or any mixture dominate the market. Overall ethanol accounts for about 30-40% of fuel burned in both cities. To improve the understanding of vehicular emission impacts on aerosol composition and life cycle in these two large megacities a source apportionment study, combining online and offline measurements, was performed. Aerosols were collected for one year to capture seasonal variability at 4 sites in each city, with inorganic and organic aerosol component being sampled. Organic and elemental carbon were measured using a Sunset Laboratory Dual Optics (transmission and reflectance) Carbon Analyzer and about 22 trace elements has been measured using polarized X-Ray Fluorescence (XRF). Aerosol mass and black carbon were also measured, as well as trace gases to help in aerosol source apportionment. In Sao Paulo, the average PM2.5 mass concentration obtained varied from 9.6 to 12.2 μg m-3 for the several sites, and similar concentrations were measured in Rio de Janeiro. At all sites, organic matter (OM) has dominated fine mode aerosol concentration with 42 to 60% of the aerosol mass. EC accounted for 21 to 31% of fine mode aerosol mass concentration. Sulfate accounted for 21 to 26% of PM2.5 for the sites. Aerosol source apportionment was done with receptor analysis and integration with online data such as PTR-MS, Aethalometers, Nephelometers and ACSM helped to apportion vehicular emissions. For the 8 sites operated in Sao Paulo and Rio de Janeiro, vehicular

  2. Combustion and Emission Characteristics of Variable Compression Ignition Engine Fueled with Jatropha curcas Ethyl Ester Blends at Different Compression Ratio

    Directory of Open Access Journals (Sweden)

    Rajneesh Kumar

    2014-01-01

    Full Text Available Engine performance and emission characteristics of unmodified biodiesel fueled diesel engines are highly influenced by their ignition and combustion behavior. In this study, emission and combustion characteristics were studied when the engine operated using the different blends (B10, B20, B30, and B40 and normal diesel fuel (B0 as well as when varying the compression ratio from 16.5 : 1 to 17.5 : 1 to 18.5 : 1. The change of compression ratio from 16.5 : 1 to 18.5 : 1 resulted in 27.1%, 27.29%, 26.38%, 28.48%, and 34.68% increase in cylinder pressure for the blends B0, B10, B20, B30, and B40, respectively, at 75% of rated load conditions. Higher peak heat release rate increased by 23.19%, 14.03%, 26.32%, 21.87%, and 25.53% for the blends B0, B10, B20, B30, and B40, respectively, at 75% of rated load conditions, when compression ratio was increased from16.5 : 1 to 18.5 : 1. The delay period decreased by 21.26%, CO emission reduced by 14.28%, and NOx emission increased by 22.84% for B40 blends at 75% of rated load conditions, when compression ratio was increased from 16.5 : 1 to 18.5 : 1. It is concluded that Jatropha oil ester can be used as fuel in diesel engine by blending it with diesel fuel.

  3. Hydroxyl (6−2 airglow emission intensity ratios for rotational temperature determination

    Directory of Open Access Journals (Sweden)

    R. P. Lowe

    Full Text Available OH(6–2 Q1/P1 and R1/P1 airglow emission intensity ratios, for rotational states up to j' = 4.5, are measured to be lower than implied by transition probabilities published by various authors including Mies, Langhoff et al. and Turnbull and Lowe. Experimentally determined relative values of j' transitions yield OH(6–2 rotational temperatures 2 K lower than Langhoff et al., 7 K lower than Mies and 13 K lower than Turnbull and Lowe.Key words: Atmospheric composition and structure (airglow and aurora; pressure, density and temperature

  4. Influence of fuel type, dilution and equivalence ratio on the emission reduction from the auto-ignition in an Homogeneous Charge Compression Ignition engine

    Energy Technology Data Exchange (ETDEWEB)

    Machrafi, Hatim [UPMC Universite Paris 06, ENSCP, 11 rue de Pierre et Marie Curie, 75005 Paris (France); UPMC Universite Paris 06, Institut Jean Le Rond D' Alembert, 4 place Jussieu, 75252 Paris cedex 05 (France); Universite Libre de Bruxelles, TIPs - Fluid Physics, CP165/67, 50 Avenue F.D. Roosevelt, 1050 Brussels (Belgium); Cavadias, Simeon [UPMC Universite Paris 06, ENSCP, 11 rue de Pierre et Marie Curie, 75005 Paris (France); UPMC Universite Paris 06, Institut Jean Le Rond D' Alembert, 4 place Jussieu, 75252 Paris cedex 05 (France); Amouroux, Jacques [UPMC Universite Paris 06, ENSCP, 11 rue de Pierre et Marie Curie, 75005 Paris (France)

    2010-04-15

    One technology that seems to be promising for automobile pollution reduction is the Homogeneous Charge Compression Ignition (HCCI). This technology still faces auto-ignition and emission-control problems. This paper focuses on the emission problem, since it is incumbent to realize engines that pollute less. For this purpose, this paper presents results concerning the measurement of the emissions of CO, NO{sub x}, CO{sub 2}, O{sub 2} and hydrocarbons. HCCI conditions are used, with equivalence ratios between 0.26 and 0.54, inlet temperatures of 70 C and 120 C and compression ratios of 10.2 and 13.5, with different fuel types: gasoline, gasoline surrogate, diesel, diesel surrogate and mixtures of n-heptane/toluene. The effect of dilution is considered for gasoline, while the effect of the equivalence ratio is considered for all the fuels. No significant amount of NO{sub x} has been measured. It appeared that the CO, O{sub 2} and hydrocarbon emissions were reduced by decreasing the toluene content of the fuel and by decreasing the dilution. The opposite holds for CO{sub 2}. The reduction of the hydrocarbon emission appears to compete with the reduction of the CO{sub 2} emission. Diesel seemed to produce less CO and hydrocarbons than gasoline when auto-ignited. An example of emission reduction control is presented in this paper. (author)

  5. Nitrous oxide emissions from yellow brown soil as affected by incorporation of crop residues with different carbon-to-nitrogen ratios: a case study in central China.

    Science.gov (United States)

    Lin, Shan; Iqbal, Javed; Hu, Ronggui; Shaaban, Muhammad; Cai, Jianbo; Chen, Xi

    2013-08-01

    To investigate the influence of crop residues decomposition on nitrous oxide (N2O) emission, a field study was performed with application of crop residues with different C:N ratios in a bare yellow brown soil at the experimental station of Zhangjiachong at Zigui, China. We set up six experimental treatments: no crop residue (CK), rapeseed cake (RC), potato stalk (PS), rice straw (RS), wheat straw (WS), and corn straw (CS). The carbon (C) to nitrogen (N) ratios of these crop residues were 7.5, 32.9, 40.4, 65.7, and 90.9, respectively. Nitrous oxide fluxes were measured using a static closed chamber method. N2O emissions were significantly enhanced by incorporation of crop residues. Cumulative N2O emissions negatively correlated with C:N ratio (R (2) = 0.9821) of the crop residue, but they were positively correlated with average concentrations of dissolved organic carbon and microbial biomass carbon. Nitrogen emission fraction, calculated as N2O-N emissions originated from the crop residues N, positively correlated with C:N ratio of the residues (P emissions because a significant correlation (P emissions in all treatments except the control. In contrast, a significant relationship between soil moisture and N2O emissions was found in the control only. Furthermore, N2O emission significantly correlated (P carbon and nitrogen contents can significantly alter soil N2O flux rates; and (2) soil biotic as well as abiotic variables are critical in determining soil-atmospheric N2O emissions after crop residue incorporation into soil.

  6. Polar and non-polar organic aerosols from large-scale agricultural-waste burning emissions in Northern India: Implications to organic mass-to-organic carbon ratio.

    Science.gov (United States)

    Rajput, Prashant; Sarin, M M

    2014-05-01

    This study focuses on characteristics of organic aerosols (polar and non-polar) and total organic mass-to-organic carbon ratio (OM/OC) from post-harvest agricultural-waste (paddy- and wheat-residue) burning emissions in Northern India. Aerosol samples from an upwind location (Patiala: 30.2°N, 76.3°E) in the Indo-Gangetic Plain were analyzed for non-polar and polar fractions of organic carbon (OC1 and OC2) and their respective mass (OM1 and OM2). On average, polar organic aerosols (OM2) contribute nearly 85% of the total organic mass (OM) from the paddy- and wheat-residue burning emissions. The water-soluble-OC (WSOC) to OC2 ratio, within the analytical uncertainty, is close to 1 from both paddy- and wheat-residue burning emissions. However, temporal variability and relatively low WSOC/OC2 ratio (Av: 0.67±0.06) is attributed to high moisture content and poor combustion efficiency during paddy-residue burning, indicating significant contribution (∼30%) of aromatic carbon to OC2. The OM/OC ratio for non-polar (OM1/OC1∼1.2) and polar organic aerosols (OM2/OC2∼2.2), hitherto unknown for open agricultural-waste burning emissions, is documented in this study. The total OM/OC ratio is nearly identical, 1.9±0.2 and 1.8±0.2, from paddy- and wheat-residue burning emissions. Copyright © 2013 Elsevier Ltd. All rights reserved.

  7. Effects of N source concentration and NH4(+)/NO3(-) ratio on phenylethanoid glycoside pattern in tissue cultures of Plantago lanceolata L.: a metabolomics driven full-factorial experiment with LC-ESI-MS(3.).

    Science.gov (United States)

    Gonda, Sándor; Kiss-Szikszai, Attila; Szűcs, Zsolt; Máthé, Csaba; Vasas, Gábor

    2014-10-01

    Tissue cultures of a medicinal plant, Plantago lanceolata L. were screened for phenylethanoid glycosides (PGs) and other natural products (NPs) with LC-ESI-MS(3). The effects of N source concentration and NH4(+)/NO3(-) ratio were evaluated in a full-factorial (FF) experiment. N concentrations of 10, 20, 40 and 60mM, and NH4(+)/NO3(-) ratios of 0, 0.11, 0.20 and 0.33 (ratio of NH4(+) in total N source) were tested. Several peaks could be identified as PGs, of which, 16 could be putatively identified from the MS/MS/MS spectra. N source concentration and NH4(+)/NO3(-) ratio had significant effects on the metabolome, their effects on individual PGs were different despite these metabolites were of the same biosynthethic class. Chief PGs were plantamajoside and acteoside (verbascoside), their highest concentrations were 3.54±0.83% and 1.30±0.40% of dry weight, on media 10(0.33) and 40(0.33), respectively. NH4(+)/NO3(-) ratio and N source concentration effects were examined on a set of 89 NPs. For most NPs, high increases in abundance were observed compared to Murashige-Skoog medium. Abundances of 42 and 10 NPs were significantly influenced by the N source concentration and the NH4(+)/NO3(-) ratio, respectively. Optimal media for production of different NP clusters were 10(0), 10(0.11) and 40(0.33). Interaction was observed between NH4(+)/NO3(-) ratio and N source concentration for many NPs. It was shown in simulated experiments, that one-factor at a time (OFAT) experimental designs lead to sub-optimal media compositions for production of many NPs, and alternative experimental designs (e.g. FF) should be preferred when optimizing medium N source for optimal yield of NPs. If using OFAT, the N source concentration is to be optimized first, followed by NH4(+)/NO3(-) ratio, as this reduces the likeliness of suboptimal yield results. Copyright © 2014 Elsevier Ltd. All rights reserved.

  8. The Prestudy for Studying Inorganic Nutrient Metabolism in Humans : the Aplication of ICP-MS for Determination of Stable Isotope Ratio of Fe and Zn

    International Nuclear Information System (INIS)

    Rukihati; Sumadjo

    2001-01-01

    A method is described for the determination of isotope ratio of Fe and Zn by means of inductively coupled plasma-mass spectrometry (ICP-MS). The mass spectrometer was operated in low resolution mode to provide maximal sensitivity. Typical conditions for operations were: plasma power 0.85 k W, reflected power 56 Fe/ 54 Fe, 57 Fe/ 54 Fe, 58 Fe/ 54 Fe, dan 64 Zn/ 67 Zn, 66 Zn/ 67 Zn, 68 Zn/ 67 Zn, 70 Zn/ 67 Zn measured by ICP-MS showed a good level of agreement with TIMS (thermal ionization mass spectrometry). This method was prepared for studying the absorption and/or metabolism of inorganic nutrients in humans. (author)

  9. Selective-Reagent-Ionization Mass Spectrometry: New Prospects for Atmospheric Research

    Science.gov (United States)

    Sulzer, Philipp; Jordan, Alfons; Hartungen, Eugen; Hanel, Gernot; Jürschik, Simone; Herbig, Jens; Märk, Lukas; Märk, Tilmann D.

    2014-05-01

    Proton-Transfer-Reaction Mass Spectrometry (PTR-MS), which was introduced to the scientific community in the 1990's, has quickly evolved into a well-established technology for atmospheric research and environmental chemistry [1]. Advantages of PTR-MS are i) high sensitivities of several hundred cps/ppbv, ii) detection limits at or below the pptv level, iii) direct injection sampling (i.e. no sample preparation), iv) response times in the 100 ms regime and v) online quantification. However, one drawback is a somehow limited selectivity, as in case of quadrupole mass filter based instruments only information about nominal m/z are available. In Time-Of-Flight (TOF) mass analyzer based instruments selectivity is drastically increased by a high mass resolution of up to 8000 m/Δm, but e.g. isomers still cannot be separated. In 2009 we introduced an advanced version of PTR-MS, which permits switching the reagent ions from H3O+ to NO+ and O2+, respectively [2]. This novel type of instrumentation was called Selective-Reagent-Ionization Mass Spectrometry (SRI-MS) and has been successfully used to separate isomers, e.g. the biogenic compounds isoprene and 2-methyl-3-buten-2-ol as shown by Karl et al. [3]. Switching the reagent ions dramatically increases selectivity and thus applicability of SRI-MS in atmospheric research. Here we report on the latest results utilizing an even more advanced embodiment of SRI-MS enabling the use of the additional reagent ions Kr+ and Xe+ [4]. With this technology important atmospheric compounds, such as CO2, CO, CH4, O2, etc. can be quantified and selectivity is increased even further. We present comparison data between diesel and gasoline car exhaust gases and quantitative data on indoor air for these compounds, which are not detectable with classical PTR-MS. Additionally, we show very recent examples of isomers which cannot be separated with PTR-MS but can clearly be distinguished with SRI-MS. Finally, we give an overview of ongoing SRI-MS

  10. IsoMS: automated processing of LC-MS data generated by a chemical isotope labeling metabolomics platform.

    Science.gov (United States)

    Zhou, Ruokun; Tseng, Chiao-Li; Huan, Tao; Li, Liang

    2014-05-20

    A chemical isotope labeling or isotope coded derivatization (ICD) metabolomics platform uses a chemical derivatization method to introduce a mass tag to all of the metabolites having a common functional group (e.g., amine), followed by LC-MS analysis of the labeled metabolites. To apply this platform to metabolomics studies involving quantitative analysis of different groups of samples, automated data processing is required. Herein, we report a data processing method based on the use of a mass spectral feature unique to the chemical labeling approach, i.e., any differential-isotope-labeled metabolites are detected as peak pairs with a fixed mass difference in a mass spectrum. A software tool, IsoMS, has been developed to process the raw data generated from one or multiple LC-MS runs by peak picking, peak pairing, peak-pair filtering, and peak-pair intensity ratio calculation. The same peak pairs detected from multiple samples are then aligned to produce a CSV file that contains the metabolite information and peak ratios relative to a control (e.g., a pooled sample). This file can be readily exported for further data and statistical analysis, which is illustrated in an example of comparing the metabolomes of human urine samples collected before and after drinking coffee. To demonstrate that this method is reliable for data processing, five (13)C2-/(12)C2-dansyl labeled metabolite standards were analyzed by LC-MS. IsoMS was able to detect these metabolites correctly. In addition, in the analysis of a (13)C2-/(12)C2-dansyl labeled human urine, IsoMS detected 2044 peak pairs, and manual inspection of these peak pairs found 90 false peak pairs, representing a false positive rate of 4.4%. IsoMS for Windows running R is freely available for noncommercial use from www.mycompoundid.org/IsoMS.

  11. Changes of the carbon dioxide emissions and the overshoot ratio resulting from the implementation of the 2nd Energy Master Plan in the Republic of Korea

    International Nuclear Information System (INIS)

    Yeo, M.J.; Kim, Y.P.

    2016-01-01

    Based on the national greenhouse gas emission reduction target for 2030 (“GHG target for 2030″) and the 2nd Energy Master Plan (“2nd EMP”), several power mix configuration scenarios were tested to estimate the sensitivity of the carbon dioxide emissions and the ‘overshoot ratio’, which is the ratio of ecological footprint to biocapacity. It would be only possible to achieve the GHG target for 2030 if the fraction of non-emission energy be more than 70% of the total input primary energy for power generation with the current conversion efficiency (40%). Even the conversion efficiency is changed to 50%, still the carbon dioxide emissions are larger than the targeted carbon dioxide emissions from the energy sector. The overshoot ratio would still increase from 5.9 in 2009 to 7.6 in 2035 even with the successful implementation of the 2nd EMP. Thus, additional efforts to reduce the carbon dioxide emissions and the overshoot ratio from the energy sector are required beyond adjusting the supply mix configuration for power generation and the conversion efficiency. Policies and programs encouraging the changes in consumer behavior toward reduction of goods consumption and energy savings are expected to impact on reducing the carbon dioxide emissions and the overshoot ratio. - Highlights: •The overshoot ratio will increase in 2035 even if the 2nd EMP is fully implemented. •Power mix configuration changes would not be enough to achieve the GHG target. •Increasing the conversion efficiency is good in long-term to achieve the GHG target.

  12. Aromatic hydrocarbons at urban, sub-urban, rural (8°52'N; 67°19'W) and remote sites in Venezuela

    Science.gov (United States)

    Holzinger, R.; Kleiss, B.; Donoso, L.; Sanhueza, E.

    Using the novel on-line proton transfer reaction mass spectrometry (PTR-MS) technique, atmospheric concentrations of benzene, toluene, xylenes, and C 9-benzenes were measured in Caracas (urban), Altos de Pipe (sub-urban), Calabozo (rural) and Parupa (remote), during various campaigns in 1999 and 2000. Average daytime mixing ratios measured in Caracas are 1.1, 3.2, 3.7, and 2.7 nmol/mol for benzene, toluene, xylenes, and C 9-benzenes. At the sub-urban site, located only few km from Caracas, relatively low levels (˜20% of the levels measured in Caracas) of these aromatic hydrocarbons were observed. At the rural site during the dry season, higher concentrations of benzene (0.15 nmol/mol) were recorded, whereas those of toluene (0.08 nmol/mol) were lower during that time. The aromatic hydrocarbon ratios in the wet season (benzene: 0.08 nmol/mol; toluene: 0.09 nmol/mol) are consistent with an aged urban plume, whereas biomass burning emissions dominate during the dry season. From rural and urban [benzene]/[toluene] ratios a mean HO concentration of 2.6×10 6 molecules/cm 3 was estimated during the wet season. This value must be considered an overestimate because it does not account for background concentrations which are likely for benzene and toluene. At the remote "La Gran Sabana" region (Parupa) very low mixing ratios (0.031 and 0.015 nmol/mol for benzene and toluene) are showing the pristine region to be unaffected by local sources. From the [benzene]/[toluene] ratio we deduced, that "urban" air arriving from the coastline (350 km) is likely mixed with air containing some background of benzene and toluene. Urban emissions (automobiles) should be the major source of aromatic compounds, however, during the dry season biomass burning seems to make an important contribution.

  13. Influence of the overfire air ratio on the NO(x) emission and combustion characteristics of a down-fired 300-MW(e) utility boiler.

    Science.gov (United States)

    Ren, Feng; Li, Zhengqi; Chen, Zhichao; Fan, Subo; Liu, Guangkui

    2010-08-15

    Down-fired boilers used to burn low-volatile coals have high NO(x) emissions. To find a way of solving this problem, an overfire air (OFA) system was introduced on a 300 MW(e) down-fired boiler. Full-scale experiments were performed on this retrofitted boiler to explore the influence of the OFA ratio (the mass flux ratio of OFA to the total combustion air) on the combustion and NO(x) emission characteristics in the furnace. Measurements were taken of gas temperature distributions along the primary air and coal mixture flows, average gas temperatures along the furnace height, concentrations of gases such as O(2), CO, and NO(x) in the near-wall region and carbon content in the fly ash. Data were compared for five different OFA ratios. The results show that as the OFA ratio increases from 12% to 35%, the NO(x) emission decreases from 1308 to 966 mg/Nm(3) (at 6% O(2) dry) and the carbon content in the fly ash increases from 6.53% to 15.86%. Considering both the environmental and economic effect, 25% was chosen as the optimized OFA ratio.

  14. ICP-MS as the method of the determination of gallium, indium and thallium isotope ratios in the studies of isotope effects in the chromatography systems

    International Nuclear Information System (INIS)

    Herdzik, I.

    2006-01-01

    The procedure of the determination of gallium, indium and thallium isotope ratios and its application to the studies of the isotope effects in chromatography systems by the ICP-MS method (inductively coupled plasma-mass spectrometry) are presented. It was shown that it is possible to determine the isotope ratios of gallium ( 69/71 Ga), indium ( 113/115 In) and thallium ( 203/205 Tl) with the relative standard deviation 0.03-0.07%. Such precision appeared to be sufficient to calculate the unit separation factors in the column chromatographic processes. (author) [pl

  15. Fluxes of biogenic volatile organic compounds measured and modelled above a Norway spruce forest

    Science.gov (United States)

    Juráň, Stanislav; Fares, Silvano; Pallozzi, Emanuele; Guidolotti, Gabriele; Savi, Flavia; Alivernini, Alessandro; Calfapietra, Carlo; Večeřová, Kristýna; Křůmal, Kamil; Večeřa, Zbyněk; Cudlín, Pavel; Urban, Otmar

    2016-04-01

    Fluxes of biogenic volatile organic compounds (BVOCs) were investigated at Norway spruce forest at Bílý Kříž in Beskydy Mountains of the Czech Republic during the summer 2014. A proton-transfer-reaction-time-of-flight mass spectrometer (PTR-TOF-MS, Ionicon Analytik, Austria) has been coupled with eddy-covariance system. Additionally, Inverse Lagrangian Transport Model has been used to derive fluxes from concentration gradient of various monoterpenes previously absorbed into n-heptane by wet effluent diffusion denuder with consequent quantification by gas chromatography with mass spectrometry detection. Modelled data cover each one day of three years with different climatic conditions and previous precipitation patterns. Model MEGAN was run to cover all dataset with monoterpene fluxes and measured basal emission factor. Highest fluxes measured by eddy-covariance were recorded during the noon hours, represented particularly by monoterpenes and isoprene. Inverse Lagrangian Transport Model suggests most abundant monoterpene fluxes being α- and β-pinene. Principal component analysis revealed dependencies of individual monoterpene fluxes on air temperature and particularly global radiation; however, these dependencies were monoterpene specific. Relationships of monoterpene fluxes with CO2 flux and relative air humidity were found to be negative. MEGAN model correlated to eddy-covariance PTR-TOF-MS measurement evince particular differences, which will be shown and discussed. Bi-directional fluxes of oxygenated short-chain volatiles (methanol, formaldehyde, acetone, acetaldehyde, formic acid, acetic acid, methyl vinyl ketone, methacrolein, and methyl ethyl ketone) were recorded by PTR-TOF-MS. Volatiles of anthropogenic origin as benzene and toluene were likely transported from the most benzene polluted region in Europe - Ostrava city and adjacent part of Poland around Katowice, where metallurgical and coal mining industries are located. Those were accumulated during

  16. Are Polyatomic Interferences, Cross Contamination, Mixing-Effect, etc., Obstacles for the Use of Laser Ablation-ICP-MS Coupling as an Operational Technique for Uranium Isotope Ratio Particle Analysis?

    International Nuclear Information System (INIS)

    Donard, A.; Pointurier, F.; Pecheyran, C.

    2015-01-01

    Analysis of ''environmental samples'', which consists in dust collected with cotton clothes wiped by inspectors on surfaces inside declared nuclear facilities, is a key tool for safeguards. Although two methods (fission tracks-TIMS and SIMS) are already used routinely to determine the isotopic composition of uranium particles, the laser ablationinductively coupled plasma mass spectrometry (LA-ICP-MS) coupling has been proven to be an interesting option thanks to its rapidity, high sensitivity and high signal/noise ratio. At CEA and UPPA, feasibility of particle analysis using a nanosecond LA device and a quadrupole ICP-MS has been demonstrated. However, despite the obvious potential of LA-ICP-MS for particle analysis, the effect of many phenomena which may bias isotope ratio measurements or lead to false detections must be investigated. Actually, environmental samples contain many types of non-uranium particles (organic debris, iron oxides, etc.) that can form molecular interferences and induce the risk of isotopic measurement bias, especially for minor isotopes (234U, 236U). The influence of these polyatomic interferences on the measurements will be discussed. Moreover, different uranium isotopic compositions can be found in the same sample. Therefore, risks of memory effect and of particle-toparticle cross-contamination by the deposition of ablation debris around the crater have also been investigated. This study has been conducted by using a femtosecond laser ablation device coupled to a high sensitivity sector field ICP-MS. Particles were fixed onto the discs with collodion and were located thanks to their fission tracks so that micrometric particles can be analyzed separately. All uranium isotope ratios were measured. Results are compared with the ones obtained with the fission tracks-TIMS technique on other deposition discs from the same sample. Performance of the method in terms of accuracy, precision, and detection limits are estimated

  17. High-aspect-ratio HfC nanobelts accompanied by HfC nanowires: Synthesis, characterization and field emission properties

    Energy Technology Data Exchange (ETDEWEB)

    Tian, Song, E-mail: tiansong22@126.com [State Key Laboratory of Solidification Processing, Northwestern Polytechnical University, Xi’an 710072 (China); School of Materials Science and Engineering, Chongqing Jiaotong University, Chongqing 400074 (China); Zhang, Yulei; Ren, Jincui; Qiang, Xinfa; Zhang, Shouyang [State Key Laboratory of Solidification Processing, Northwestern Polytechnical University, Xi’an 710072 (China); Li, Hejun, E-mail: lihejun@nwpu.edu.cn [State Key Laboratory of Solidification Processing, Northwestern Polytechnical University, Xi’an 710072 (China)

    2017-04-30

    Highlights: • HfC naobelts accompanied by HfC nanowires were synthesized by a catalytic CVD method. • HfC nanobelts as a novel structure of HfC ceramic are reported for the first time. • HfC nanobelts have 100–200 μm in lengths and reach up to 10 μm in widths. • The synthesized product is promising field nanoemitters. - Abstract: As a key refractory carbide, hafnium carbide (HfC) is commonly used as structural materials while the field emission (FE) application of HfC in the field of vacuum microelectronics is almost the only one for functional material purposes. Based on its outstanding physical and chemical characteristics, HfC is identified as a potential candidate with satisfactory mechanical properties and long-term and/or high-temperature FE stability for future applications in high-performance field emitters. However, the development of HfC in various FE applications is hindered because it is not facile to fabricate large-scale low-dimensional HfC field nanoemitters. Herein, High-aspect-ratio HfC nanobelts accompanied by HfC nanowires were synthesized on a large scale by a traditional and simple catalytic chemical vapor deposition (CVD) method. Classical vapor–liquid–solid (VLS) theory was employed to explain the growth of the HfC nanowires and nanobelts along axial direction. The thin HfO{sub 2} shell and thin C layer surrounding the nanostructures might give rise to the diameter fluctuation of HfC nanowires and the width increase of HfC nanobelts in lateral direction. Field emission results show that the high-aspect-ratio HfC nanobelts accompanied by the nanowires are promising field nanoemitters, which exhibit excellent field emission properties with a fairly low turn-on field of ∼1.5 V μm{sup −1} and a low current fluctuation less than ∼10%. This suggests that HfC ceramics with high-aspect-ratio nanostructures are ideal cathode material for various field emission applications.

  18. Chemical characterization of organic particulate matter from on-road traffic in São Paulo, Brazil

    Directory of Open Access Journals (Sweden)

    B. S. Oyama

    2016-11-01

    Full Text Available This study reports emission of organic particulate matter by light-duty vehicles (LDVs and heavy-duty vehicles (HDVs in the city of São Paulo, Brazil, where vehicles run on three different fuel types: gasoline with 25 % ethanol (called gasohol, E25, hydrated ethanol (E100, and diesel (with 5 % biodiesel. The experiments were performed at two tunnels: Jânio Quadros (TJQ, where 99 % of the vehicles are LDVs, and RodoAnel Mário Covas (TRA, where up to 30 % of the fleet are HDVs. Fine particulate matter (PM2.5 samples were collected on quartz filters in May and July 2011 at TJQ and TRA, respectively. The samples were analyzed by thermal-desorption proton-transfer-reaction mass spectrometry (TD-PTR-MS and by thermal–optical transmittance (TOT. Emission factors (EFs for organic aerosol (OA and organic carbon (OC were calculated for the HDV and the LDV fleet. We found that HDVs emitted more PM2.5 than LDVs, with OC EFs of 108 and 523 mg kg−1 burned fuel for LDVs and HDVs, respectively. More than 700 ions were identified by TD-PTR-MS and the EF profiles obtained from HDVs and LDVs exhibited distinct features. Unique organic tracers for gasoline, biodiesel, and tire wear have been tentatively identified. nitrogen-containing compounds contributed around 20 % to the EF values for both types of vehicles, possibly associated with incomplete fuel burning or fast secondary production. Additionally, 70 and 65 % of the emitted mass (i.e. the OA originates from oxygenated compounds from LDVs and HDVs, respectively. This may be a consequence of the high oxygen content of the fuel. On the other hand, additional oxygenation may occur during fuel combustion. The high fractions of nitrogen- and oxygen-containing compounds show that chemical processing close to the engine / tailpipe region is an important factor influencing primary OA emission. The thermal-desorption analysis showed that HDVs emitted compounds with higher volatility, and with

  19. Distribution, magnitudes, reactivities, ratios and diurnal patterns of volatile organic compounds in the Valley of Mexico during the MCMA 2002 & 2003 field campaigns

    Directory of Open Access Journals (Sweden)

    E. Velasco

    2007-01-01

    Full Text Available A wide array of volatile organic compound (VOC measurements was conducted in the Valley of Mexico during the MCMA-2002 and 2003 field campaigns. Study sites included locations in the urban core, in a heavily industrial area and at boundary sites in rural landscapes. In addition, a novel mobile-laboratory-based conditional sampling method was used to collect samples dominated by fresh on-road vehicle exhaust to identify those VOCs whose ambient concentrations were primarily due to vehicle emissions. Four distinct analytical techniques were used: whole air canister samples with Gas Chromatography/Flame Ionization Detection (GC-FID, on-line chemical ionization using a Proton Transfer Reaction Mass Spectrometer (PTR-MS, continuous real-time detection of olefins using a Fast Olefin Sensor (FOS, and long path measurements using UV Differential Optical Absorption Spectrometers (DOAS. The simultaneous use of these techniques provided a wide range of individual VOC measurements with different spatial and temporal scales. The VOC data were analyzed to understand concentration and spatial distributions, diurnal patterns, origin and reactivity in the atmosphere of Mexico City. The VOC burden (in ppbC was dominated by alkanes (60%, followed by aromatics (15% and olefins (5%. The remaining 20% was a mix of alkynes, halogenated hydrocarbons, oxygenated species (esters, ethers, etc. and other unidentified VOCs. However, in terms of ozone production, olefins were the most relevant hydrocarbons. Elevated levels of toxic hydrocarbons, such as 1,3-butadiene, benzene, toluene and xylenes, were also observed. Results from these various analytical techniques showed that vehicle exhaust is the main source of VOCs in Mexico City and that diurnal patterns depend on vehicular traffic in addition to meteorological processes. Finally, examination of the VOC data in terms of lumped modeling VOC classes and its comparison to the VOC lumped emissions reported in other

  20. Effects of mix ratio, moisture content and aeration rate on sulfur odor emissions during pig manure composting.

    Science.gov (United States)

    Zang, Bing; Li, Shuyan; Michel, Frederick; Li, Guoxue; Luo, Yuan; Zhang, Difang; Li, Yangyang

    2016-10-01

    Sulfur compounds in swine manure can cause odor emissions during composting if conditions are not conducive to their rapid oxidation and degradation. In this study, the effects of controllable composting process variables on sulfur odor emissions were investigated. These included pig manure to corn stalk mix ratio (0.7:1, 1.5:1 and 2.2:1dw basis), initial moisture content (60%, 65%, 70% and 75%) and aeration rate (1.0, 2.0, 3.0 and 4.0m(3)m(-3)h(-1)). The compounds measured were carbonyl sulfide, carbon disulfide, hydrogen sulfide, methyl mercaptan, ethyl mercaptan, diethyl sulfide, dimethyl sulfide (Me2S) and dimethyl disulfide (Me2SS). The results showed that total sulfur losses ranged from 3.9% to 18.3% after 26days of composting. Me2S and Me2SS were the primary (>59.61%) sulfur compounds released during this period. After turning, emission rates of both Me2S and Me2SS increased. Emissions of the other six sulfur compounds were low and inconsistent during composting. Within the compost, feedstock mix ratio significantly influenced the concentration of Me2SS, while aeration rate significantly affected Me2S concentration (pMoisture content did not have a significant effect on the concentrations of either of these two compounds. Concentrations of sulfur odor compounds were the lowest at the highest aeration rate. Therefore, high aeration rates during the thermophilic phase, especially after turning, are recommended to minimize sulfur odors produced during swine manure composting. Copyright © 2016 Elsevier Ltd. All rights reserved.

  1. Direct isotope ratio measurement of uranium metal by emission spectrometry on a laser-produced plasma

    International Nuclear Information System (INIS)

    Pietsch, W.; Petit, A.; Briand, A.

    1995-01-01

    The method of Optical Emission Spectrometry on a Laser-Produced Plasma (OES/LPP) at reduced pressure has been studied for the determination of the uranium isotope ratio ( 235 U/ 238 U). Spectral profiles of the investigated transition U-II 424.437 nm show the possibility to obtain an isotopic spectral resolution in a laser-produced plasma under exactly defined experimental conditions. Spectroscopic data and results are presented. (author)

  2. Performance and emission of generator Diesel engine using methyl esters of palm oil and diesel blends at different compression ratio

    Science.gov (United States)

    Aldhaidhawi, M.; Chiriac, R.; Bădescu, V.; Pop, H.; Apostol, V.; Dobrovicescu, A.; Prisecaru, M.; Alfaryjat, A. A.; Ghilvacs, M.; Alexandru, A.

    2016-08-01

    This study proposes engine model to predicate the performance and exhaust gas emissions of a single cylinder four stroke direct injection engine which was fuelled with diesel and palm oil methyl ester of B7 (blends 7% palm oil methyl ester with 93% diesel by volume) and B10. The experiment was conducted at constant engine speed of 3000 rpm and different engine loads operations with compression ratios of 18:1, 20:1 and 22:1. The influence of the compression ratio and fuel typeson specific fuel consumption and brake thermal efficiency has been investigated and presented. The optimum compression ratio which yields better performance has been identified. The result from the present work confirms that biodiesel resulting from palm oil methyl ester could represent a superior alternative to diesel fuel when the engine operates with variable compression ratios. The blends, when used as fuel, result in a reduction of the brake specific fuel consumption and brake thermal efficiency, while NOx emissions was increased when the engine is operated with biodiesel blends.

  3. Method-MS. Final report

    International Nuclear Information System (INIS)

    Skipperud, L.; Popic, J.M.; Roos, P.; Salminen, S.; Nygren, U.; Sigmarsson, O.; Palsson, S.E.

    2011-05-01

    Radiometric determination methods, such as alpha spectrometry require long counting times when low activities are to be determined. Mass spectrometric techniques as Inductively Coupled Plasma Mass Spectrometry (ICP-MS), Thermal Ionisation Mass Spectrometry (TIMS) and Accelerator Mass Spectrometry (AMS) have shown several advantages compared to traditional methods when measuring long-lived radionuclides. Mass spectrometric methods for determination of very low concentrations of elemental isotopes, and thereby isotopic ratios, have been developed using a variety of ion sources. Although primarily applied to the determination of the lighter stable element isotopes and radioactive isotopes in geological studies, the techniques can equally well be applied to the measurement of activity concentrations of long-lived low-level radionuclides in various samples using 'isotope dilution' methods such as those applied in inductively coupled plasma mass spectrometry (ICP-MS). Due to the low specific activity of long-lived radionuclides, many of these are more conveniently detected using mass spectrometric techniques. Mass spectrometry also enables the individual determination of Pu-239 and Pu-240, which cannot be obtained by alpha spectrometry. Inductively Coupled Plasma Mass Spectrometry (ICP-MS) are rapidly growing techniques for the ultra-trace analytical determination of stable and long-lived isotopes and have a wide potential within environmental science, including ecosystem tracers and radio ecological studies. Such instrumentation, of course needs good radiochemical separation, to give best performance. The objectives of the project is to identify current needs and problems within low-level determination of long-lived radioisotopes by ICP-MS, to perform intercalibration and development and improvement of ICP-MS methods for the measurement of radionuclides and isotope ratios and to develop new methods based on modified separation chemistry applied to new auxiliary

  4. Method-MS. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Skipperud, L.; Popic, J.M. (Norwegian Univ. of Life Science (UMB), Isotope Lab. (Norway)); Roos, P. (Technical Univ. of Denmark, Risoe National Lab. for Sustainable Energy, Roskilde (Denmark)); Salminen, S. (Univ. of Helsinki (UH) (Finland)); Nygren, U. (Swedish Defence Research Agency (FOI) (Sweden)); Sigmarsson, O.; Palsson, S.E. (Univ. of Iceland/Icelandic Radiation Protection Institute (Iceland))

    2011-05-15

    Radiometric determination methods, such as alpha spectrometry require long counting times when low activities are to be determined. Mass spectrometric techniques as Inductively Coupled Plasma Mass Spectrometry (ICP-MS), Thermal Ionisation Mass Spectrometry (TIMS) and Accelerator Mass Spectrometry (AMS) have shown several advantages compared to traditional methods when measuring long-lived radionuclides. Mass spectrometric methods for determination of very low concentrations of elemental isotopes, and thereby isotopic ratios, have been developed using a variety of ion sources. Although primarily applied to the determination of the lighter stable element isotopes and radioactive isotopes in geological studies, the techniques can equally well be applied to the measurement of activity concentrations of long-lived low-level radionuclides in various samples using 'isotope dilution' methods such as those applied in inductively coupled plasma mass spectrometry (ICP-MS). Due to the low specific activity of long-lived radionuclides, many of these are more conveniently detected using mass spectrometric techniques. Mass spectrometry also enables the individual determination of Pu-239 and Pu-240, which cannot be obtained by alpha spectrometry. Inductively Coupled Plasma Mass Spectrometry (ICP-MS) are rapidly growing techniques for the ultra-trace analytical determination of stable and long-lived isotopes and have a wide potential within environmental science, including ecosystem tracers and radio ecological studies. Such instrumentation, of course needs good radiochemical separation, to give best performance. The objectives of the project is to identify current needs and problems within low-level determination of long-lived radioisotopes by ICP-MS, to perform intercalibration and development and improvement of ICP-MS methods for the measurement of radionuclides and isotope ratios and to develop new methods based on modified separation chemistry applied to new

  5. Characteristic Study of Some Different Kinds of Coal Particles Combustion with Online TG-MS-FTIR

    Science.gov (United States)

    Pan, Guanfu

    2018-01-01

    Four kinds of pulverized coal samples from China and Indonesia were studied by thermogravimetry coupled with mass spectrometry and fourier transform infrared spectroscopy (TG-MS-FTIR). The thermal behaviors and gaseous emissions of these coals were analyzed in this work. The results indicate that the relative lower values of H/C ratios, which normally represent the degree of aromatization and ring condensation in coal samples, could lead to the relative more intense thermal reaction. The time-evolved profiles of some typical gas products (i.e., CO, SO2, CH4, NO, NO2, NH3 and etc.) were provided by TG-MS-FTIR, and their variations are different. For all the samples, the releases of SO2 and COS can be found at lower temperature than those of NO and CO. As the temperature increases, the possible conversion of NO2 and NH3 to NO is deduced in this work.

  6. Total OH reactivity measurements using a new fast Gas Chromatographic Photo-Ionization Detector (GC-PID

    Directory of Open Access Journals (Sweden)

    V. Sinha

    2012-12-01

    Full Text Available The primary and most important oxidant in the atmosphere is the hydroxyl radical (OH. Currently OH sinks, particularly gas phase reactions, are poorly constrained. One way to characterize the overall sink of OH is to measure directly the ambient loss rate of OH, the total OH reactivity. To date, direct measurements of total OH reactivity have been either performed using a Laser-Induced Fluorescence (LIF system ("pump-and-probe" or "flow reactor" or the Comparative Reactivity Method (CRM with a Proton-Transfer-Reaction Mass Spectrometer (PTR-MS. Both techniques require large, complex and expensive detection systems. This study presents a feasibility assessment for CRM total OH reactivity measurements using a new detector, a Gas Chromatographic Photoionization Detector (GC-PID. Such a system is smaller, more portable, less power consuming and less expensive than other total OH reactivity measurement techniques.

    Total OH reactivity is measured by the CRM using a competitive reaction between a reagent (here pyrrole with OH alone and in the presence of atmospheric reactive molecules. The new CRM method for total OH reactivity has been tested with parallel measurements of the GC-PID and the previously validated PTR-MS as detector for the reagent pyrrole during laboratory experiments, plant chamber and boreal field studies. Excellent agreement of both detectors was found when the GC-PID was operated under optimum conditions. Time resolution (60–70 s, sensitivity (LOD 3–6 s−1 and overall uncertainty (25% in optimum conditions for total OH reactivity were similar to PTR-MS based total OH reactivity measurements. One drawback of the GC-PID system was the steady loss of sensitivity and accuracy during intensive measurements lasting several weeks, and a possible toluene interference. Generally, the GC-PID system has been shown to produce closely comparable results to the PTR-MS and thus in suitable environments (e.g. forests it

  7. Measurement of strontium isotope ratio in nitric acid extract of peanut testa by ICP-Q-MS after removal of Rb by extraction with pure water.

    Science.gov (United States)

    Zhu, Yanbei; Hioki, Akiharu; Chiba, Koichi

    2014-02-01

    The difference in the distributions of Sr and Rb in peanut seeds was utilized to develop a precise method for Sr isotope ratio measurement by inductively coupled plasma quadruple mass spectrometry (ICP-Q-MS). The testa instead of the whole peanut seed was selected as the sample because apparent enrichment of Sr in comparison to Rb was found in the testa. Furthermore, Rb in the testa was removed by pure water extraction with the aid of sonication to remove the isobaric interference in Sr isotope ratio measurement. The testa taken from one peanut seed was treated as one sample for the analysis. After optimization of the operating conditions, pure water (10 mL for each sample) extraction in 30 min with sonication was able to remove over 95% of Rb in the testa, while after the Rb removal Sr could be completely extracted using 10 mL of 0.3 mol L(-1) HNO3 for each sample. The integration time in ICP-Q-MS measurement was optimized to achieve a lower measurement uncertainty in a shorter time; the results showed that 1s was required and enough for the precise measurement of Sr isotope ratios giving a relative standard uncertainty (n=10) of ca. 0.1%. The present method was applied to peanut seeds grown in Japan, China, USA, India, and South Africa. © 2013 Published by Elsevier B.V.

  8. The Evolution of Normal Galaxy X-Ray Emission Through Cosmic History: Constraints from the 6 MS Chandra Deep Field-South

    Science.gov (United States)

    Lehmer, B. D.; Basu-Zych, A. R.; Mineo, S.; Brandt, W. N.; Eurfrasio, R. T.; Fragos, T.; Hornschemeier, A. E.; Lou, B.; Xue, Y. Q.; Bauer, F. E.; hide

    2016-01-01

    We present measurements of the evolution of normal-galaxy X-ray emission from z (is) approx. 0-7 using local galaxies and galaxy samples in the approx. 6 Ms Chandra Deep Field-South (CDF-S) survey. The majority of the CDF-S galaxies are observed at rest-frame energies above 2 keV, where the emission is expected to be dominated by X-ray binary (XRB) populations; however, hot gas is expected to provide small contributions to the observed-frame (is) less than 1 keV emission at z (is) less than 1. We show that a single scaling relation between X-ray luminosity (L(sub x)) and star-formation rate (SFR) literature, is insufficient for characterizing the average X-ray emission at all redshifts. We establish that scaling relations involving not only SFR, but also stellar mass and redshift, provide significantly improved characterizations of the average X-ray emission from normal galaxy populations at z (is) approx. 0-7. We further provide the first empirical constraints on the redshift evolution of X-ray emission from both low-mass XRB (LMXB) and high-mass XRB (HMXB) populations and their scalings with stellar mass and SFR, respectively. We find L2 -10 keV(LMXB)/stellar mass alpha (1+z)(sub 2-3) and L2 -10 keV(HMXB)/SFR alpha (1+z), and show that these relations are consistent with XRB population-synthesis model predictions, which attribute the increase in LMXB and HMXB scaling relations with redshift as being due to declining host galaxy stellar ages and metallicities, respectively. We discuss how emission from XRBs could provide an important source of heating to the intergalactic medium in the early universe, exceeding that of active galactic nuclei.

  9. Combining emission inventory and isotope ratio analyses for quantitative source apportionment of heavy metals in agricultural soil.

    Science.gov (United States)

    Chen, Lian; Zhou, Shenglu; Wu, Shaohua; Wang, Chunhui; Li, Baojie; Li, Yan; Wang, Junxiao

    2018-08-01

    Two quantitative methods (emission inventory and isotope ratio analysis) were combined to apportion source contributions of heavy metals entering agricultural soils in the Lihe River watershed (Taihu region, east China). Source apportionment based on the emission inventory method indicated that for Cd, Cr, Cu, Pb, and Zn, the mean percentage input from atmospheric deposition was highest (62-85%), followed by irrigation (12-27%) and fertilization (1-14%). Thus, the heavy metals were derived mainly from industrial activities and traffic emissions. For Ni the combined percentage input from irrigation and fertilization was approximately 20% higher than that from atmospheric deposition, indicating that Ni was mainly derived from agricultural activities. Based on isotope ratio analysis, atmospheric deposition accounted for 57-93% of Pb entering soil, with the mean value of 69.3%, which indicates that this was the major source of Pb entering soil in the study area. The mean contributions of irrigation and fertilization to Pb pollution of soil ranged from 0% to 10%, indicating that they played only a marginally important role. Overall, the results obtained using the two methods were similar. This study provides a reliable approach for source apportionment of heavy metals entering agricultural soils in the study area, and clearly have potential application for future studies in other regions. Copyright © 2018 Elsevier Ltd. All rights reserved.

  10. Precise determination of Pb isotope ratios by simple double spike MC-ICP-MS technique without Tl addition

    Digital Repository Service at National Institute of Oceanography (India)

    Makishima, A.; Nath, B.N.; Nakamura, E.

    A double-spike multicollector ICP-MS (DS-MC-ICP-MS) technique for Pb isotope analysis without Tl addition is established and its analytical performance is examined in detail. This simple DS-MC-ICP-MS technique using 20 ng ml sup(-1) gave averages...

  11. Blue and red dual emission nanophosphor CaMgSi2O6:Eun+; crystal structure and electronic configuration

    International Nuclear Information System (INIS)

    Pawar, A.U.; Jadhav, Abhijit P.; Pal, U.; Kim, Byung Kyu; Kang, Young Soo

    2012-01-01

    Well dispersed Eu doped CaMgSi 2 O 6 (CMS) nanoparticles of 12–19 nm average sizes were synthesized by the co-precipitation method using different ratios of water and ethanol mixture as a solvent and subsequent air annealing. While ethanol as solvent produced pure CMS in monoclinic phase, pure water produced Ca 2 MgSi 2 O 7 (C2MS) and CMS in the mixed phase. Apart from the composition of CMS and C2MS, concentration and ionization state of the activator depended strongly on the composition (effective dielectric constant) of the solvent. Both the blue and red emission bands could be revealed for the europium activated CMS nanoparticles using single europium precursor. Efficiency of blue and red emissions in the nanophosphors, controlled by the relative abundance of europium in Eu 2+ and Eu 3+ oxidation states, could be controlled by adjusting the water content in the solvent. The relative intensity of the red emission (615 nm) decreased with the increase of water content in the solvent. - Highlights: ► We have synthesized Eu doped CaMgSi 2 O 6 using different volume ratios of water and ethanol solvent. ► We observed Ca 2 MgSi 2 O 7 phase increases with increasing amount of water in solvent. ► Dual emission was observed using single europium precursor. ► As synthesized material can be used for wavelength conversion application.

  12. Chemical evolution of organic aerosol in Los Angeles during the CalNex 2010 study

    Directory of Open Access Journals (Sweden)

    R. Holzinger

    2013-10-01

    Full Text Available During the CalNex study (15 May to 16 June 2010 a large suite of instruments was operated at the Los Angeles area ground supersite to characterize the sources and atmospheric processing of atmospheric pollution. The thermal-desorption proton-transfer-reaction mass-spectrometer (TD-PTR-MS was deployed to an urban area for the first time and detected 691 organic ions in aerosol samples, the mean total concentration of which was estimated as 3.3 μg m−3. Based on comparison to total organic aerosol (OA measurements, we estimate that approximately 50% of the OA mass at this site was directly measured by the TD-PTR-MS. Based on correlations with aerosol mass spectrometer (AMS OA components, the ions were grouped to represent hydrocarbon-like OA (HOA, local OA (LOA, semi-volatile oxygenated OA (SV-OOA, and low volatility oxygenated OA (LV-OOA. Mass spectra and thermograms of the ion groups are mostly consistent with the assumed sources and/or photochemical origin of the OA components. The mass spectra of ions representing the primary components HOA and LOA included the highest m/z, consistent with their higher resistance to thermal decomposition, and they were volatilized at lower temperatures (~ 150 °C. Photochemical ageing weakens C-C bond strengths (also resulting in chemical fragmentation, and produces species of lower volatility (through the addition of functional groups. Accordingly the mass spectra of ions representing the oxidized OA components (SV-OOA, and LV-OOA lack the highest masses and they are volatilized at higher temperatures (250–300 °C. Chemical parameters like mean carbon number (nC, mean carbon oxidation state (OSC, and the atomic ratios O / C and H / C of the ion groups are consistent with the expected sources and photochemical processing of the aerosol components. Our data suggest that chemical fragmentation gains importance over functionalization as photochemical age of OA increases. Surprisingly, the photochemical age of

  13. Effect of compression ratio, nozzle opening pressure, engine load, and butanol addition on nanoparticle emissions from a non-road diesel engine.

    Science.gov (United States)

    Maurya, Rakesh Kumar; Saxena, Mohit Raj; Rai, Piyush; Bhardwaj, Aashish

    2018-05-01

    Currently, diesel engines are more preferred over gasoline engines due to their higher torque output and fuel economy. However, diesel engines confront major challenge of meeting the future stringent emission norms (especially soot particle emissions) while maintaining the same fuel economy. In this study, nanosize range soot particle emission characteristics of a stationary (non-road) diesel engine have been experimentally investigated. Experiments are conducted at a constant speed of 1500 rpm for three compression ratios and nozzle opening pressures at different engine loads. In-cylinder pressure history for 2000 consecutive engine cycles is recorded and averaged data is used for analysis of combustion characteristics. An electrical mobility-based fast particle sizer is used for analyzing particle size and mass distributions of engine exhaust particles at different test conditions. Soot particle distribution from 5 to 1000 nm was recorded. Results show that total particle concentration decreases with an increase in engine operating loads. Moreover, the addition of butanol in the diesel fuel leads to the reduction in soot particle concentration. Regression analysis was also conducted to derive a correlation between combustion parameters and particle number emissions for different compression ratios. Regression analysis shows a strong correlation between cylinder pressure-based combustion parameters and particle number emission.

  14. Structure Annotation and Quantification of Wheat Seed Oxidized Lipids by High-Resolution LC-MS/MS.

    Science.gov (United States)

    Riewe, David; Wiebach, Janine; Altmann, Thomas

    2017-10-01

    Lipid oxidation is a process ubiquitous in life, but the direct and comprehensive analysis of oxidized lipids has been limited by available analytical methods. We applied high-resolution liquid chromatography-mass spectrometry (LC-MS) and tandem mass spectrometry (MS/MS) to quantify oxidized lipids (glycerides, fatty acids, phospholipids, lysophospholipids, and galactolipids) and implemented a platform-independent high-throughput-amenable analysis pipeline for the high-confidence annotation and acyl composition analysis of oxidized lipids. Lipid contents of 90 different naturally aged wheat ( Triticum aestivum ) seed stocks were quantified in an untargeted high-resolution LC-MS experiment, resulting in 18,556 quantitative mass-to-charge ratio features. In a posthoc liquid chromatography-tandem mass spectrometry experiment, high-resolution MS/MS spectra (5 mD accuracy) were recorded for 8,957 out of 12,080 putatively monoisotopic features of the LC-MS data set. A total of 353 nonoxidized and 559 oxidized lipids with up to four additional oxygen atoms were annotated based on the accurate mass recordings (1.5 ppm tolerance) of the LC-MS data set and filtering procedures. MS/MS spectra available for 828 of these annotations were analyzed by translating experimentally known fragmentation rules of lipids into the fragmentation of oxidized lipids. This led to the identification of 259 nonoxidized and 365 oxidized lipids by both accurate mass and MS/MS spectra and to the determination of acyl compositions for 221 nonoxidized and 295 oxidized lipids. Analysis of 15-year aged wheat seeds revealed increased lipid oxidation and hydrolysis in seeds stored in ambient versus cold conditions. © 2017 The author(s). All Rights Reserved.

  15. A UPLC-MS/MS method for analysis of vancomycin in human cerebrospinal fluid and comparison with the chemiluminescence immunoassay.

    Science.gov (United States)

    Mei, Shenghui; Wang, Jiaqing; Zhu, Leting; Chen, Ruiling; Li, Xingang; Chen, Kai; Chen, Guangqiang; Zhou, Jianxin; Wang, Qiang; Zhao, Zhigang

    2017-08-01

    Vancomycin (VCM) is clinically used in treating patients with postoperative intracranial infections. The cerebrospinal fluid (CSF) concentration of VCM varies greatly among patients. To guide the dosage regimens, monitoring of VCM in CSF is needed. However a method for analysis of VCM in human CSF is lacking. An ultraperformance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) was developed and validated for analysis of VCM in human CSF, and the agreement of UPLC-MS/MS and chemiluminescence immunoassay (CLIA) in the analysis of CSF VCM was evaluated. The ion transitions were m/z 725.5 > 144.1 for VCM and m/z 455.2 > 308.2 for methotrexate (internal standard). The agreement between UPLC-MS/MS and CLIA was evaluated by Bland-Altman plot in 179 samples. The calibration range of the UPLC-MS/MS method was 1-400 mg/L. The inaccuracy and imprecision were -0.69-10.80% and  0.98). The 95% limit of agreement of the ratio of CLIA to UPLC-MS/MS was 61.66-107.40%. Further studies are warranted to confirm the results. Copyright © 2017 John Wiley & Sons, Ltd.

  16. Effect of gas ratio on tribological properties of sputter deposited TiN coatings

    Energy Technology Data Exchange (ETDEWEB)

    Chavda, Mahesh R., E-mail: maheshchavda1990@gmail.com [Department of Mechanical Engineering, Dr. Jivraj Mehta Institute of Technology, Mogar-388340 (India); Chauhan, Kamlesh V.; Rawal, Sushant K., E-mail: sushantrawal.me@charusat.ac.in [CHAMOS Matrusanstha Department of Mechanical Engineering, Chandubhai S. Patel Institute of Technology, Charotar University of Science and Technology (CHARUSAT), Changa-388421 (India)

    2016-05-06

    Titanium nitride (TiN) coatings were deposited on Si, corning glass, pins of mild steel (MS, ϕ3mm), aluminium (Al, ϕ4mm) and brass (ϕ6mm) substratesby DC magnetron sputtering. The argon and nitrogen (Ar:N{sub 2})gas ratio was precisely controlled by Mass Flow Controller (MFC) and was varied systematically at diffract values of 10:10,12:08, 16:04 and 18:02sccm. The structural properties of TiN coatings were characterized by X-ray diffraction (XRD) and its surface topography was studied using field emission scanning electron microscopy (FE-SEM). The tribological properties of TiN coatings were investigated using pin-on-disc tribometer.

  17. Gas phase emissions from cooking processes and their secondary aerosol production potential

    Science.gov (United States)

    Klein, Felix; Platt, Stephen; Bruns, Emily; Termime-roussel, Brice; Detournay, Anais; Mohr, Claudia; Crippa, Monica; Slowik, Jay; Marchand, Nicolas; Baltensperger, Urs; Prevot, Andre; El Haddad, Imad

    2014-05-01

    Long before the industrial evolution and the era of fossil fuels, high concentrations of aerosol particles were alluded to in heavily populated areas, including ancient Rome and medieval London. Recent radiocarbon measurements (14C) conducted in modern megacities came as a surprise: carbonaceous aerosol (mainly organic aerosol, OA), a predominant fraction of particulate matter (PM), remains overwhelmingly non-fossil despite extensive fossil fuel combustion. Such particles are directly emitted (primary OA, POA) or formed in-situ in the atmosphere (secondary OA, SOA) via photochemical reactions of volatile organic compounds (VOCs). Urban levels of non-fossil OA greatly exceed the levels measured in pristine environments strongly impacted by biogenic emissions, suggesting a contribution from unidentified anthropogenic non-fossil sources to urban OA. Positive matrix factorization (PMF) techniques applied to ambient aerosol mass spectrometer (AMS, Aerodyne) data identify primary cooking emissions (COA) as one of the main sources of primary non-fossil OA in major cities like London (Allan et al., 2010), New York (Sun et al., 2011) and Beijing (Huang et al., 2010). Cooking processes can also emit VOCs that can act as SOA precursors, potentially explaining in part the high levels of oxygenated OA (OOA) identified by the AMS in urban areas. However, at present, the chemical nature of these VOCs and their secondary aerosol production potential (SAPP) remain virtually unknown. The approach adopted here involves laboratory quantification of PM and VOC emission factors from the main primary COA emitting processes and their SAPP. Primary emissions from deep-fat frying, vegetable boiling, vegetable frying and meat cooking for different oils, meats and vegetables were analysed under controlled conditions after ~100 times dilution. A high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and a high resolution proton transfer time-of-flight mass spectrometer (PTR-ToF-MS

  18. Experimental investigation of particle emissions under different EGR ratios on a diesel engine fueled by blends of diesel/gasoline/n-butanol

    International Nuclear Information System (INIS)

    Huang, Haozhong; Liu, Qingsheng; Wang, Qingxin; Zhou, Chengzhong; Mo, Chunlan; Wang, Xueqiang

    2016-01-01

    Highlights: • The effects of EGR and blend fuels on particulate emission were studied in CI engine. • EGR ⩽ 20%, gasoline or n-butanol increases total particulate number concentration. • EGR ⩾ 30%, gasoline or n-butanol reduces total particulate number concentration. • As EGR ratio increased, the particulate mass concentrations of four fuels increased. • Gasoline or n-butanol increases the ratio of sub-25 nm particles number concentration. - Abstract: The particle emission characteristics of a high-pressure common-rail engine under different EGR conditions were investigated, using pure diesel (D100), diesel/gasoline (with a volume ratio of 70:30, D70G30), diesel/n-butanol (with a volume ratio of 70:30, D70B30) and diesel/gasoline/n-butanol (with a volume ratio of 70:15:15, D70G15B15) for combustion. Our results show that, with increasing EGR ratios, the in-cylinder pressure peak decreases and the heat release is delayed for the combustion of each fuel. At an EGR ratio of 30%, the combustion pressure peaks of D70G30, D70B30, D70G15B15 and D100 have similar values; with an EGR ratio of 40%, the combustion pressure peaks and release rate peaks of D70G30 and D70G15B15 are both lower with respect to D100. For small and medium EGR ratios (⩽20%), after the addition of gasoline and/or n-butanol to the fuel, the total particle number concentration (TPNC) increases, while both the soot emissions and the average geometric size of particles decrease. At large EGR ratios (30% and 40%), the TPNC of D70B30, D70G15B15 and D70G20 compared to D100 are reduced by a maximum amount of 74.7%, 66.7% and 28.6%, respectively. As the EGR ratio increases, the total particle mass concentration increases gradually for all four fuels. Blending gasoline or/and n-butanol into diesel induces an increase in the number concentration of sub-25 nm particles (PN25) which may be harmful in terms of health. However, the PN25 decreases with increasing the EGR ratio for all the tested fuels

  19. Molecular interaction between Methylobacterium extorquens and seedlings: growth promotion, methanol consumption, and localization of the methanol emission site.

    Science.gov (United States)

    Abanda-Nkpwatt, Daniel; Müsch, Martina; Tschiersch, Jochen; Boettner, Mewes; Schwab, Wilfried

    2006-01-01

    Four Methylobacterium extorquens strains were isolated from strawberry (Fragaria x ananassa cv. Elsanta) leaves, and one strain, called ME4, was tested for its ability to promote the growth of various plant seedlings. Seedling weight and shoot length of Nicotiana tabacum, Lycopersicon esculentum, Sinapis alba, and Fragaria vesca increased significantly in the presence of the pink-pigmented facultative methylotroph (PPFM), but the germination behaviour of seeds from six other plants was not affected. The cell-free supernatant of the bacterial culture stimulated germination, suggesting the production of a growth-promoting agent by the methylotroph. Methanol emitted from N. tabacum seedlings, as determined by proton-transfer-reaction mass spectrometry (PTR-MS), ranged from 0.4 to 0.7 ppbv (parts per billion by volume), while significantly lower levels (0.005 to 0.01 ppbv) of the volatile alcohol were measured when the seedlings were co-cultivated with M. extorquens ME4, demonstrating the consumption of the gaseous methanol by the bacteria. Additionally, by using cells of the methylotrophic yeast Pichia pastoris transformed with the pPICHS/GFP vector harbouring a methanol-sensitive promoter in combination with the green fluorescence protein (GFP) reporter gene, stomata were identified as the main source of the methanol emission on tobacco cotyledons. Methylobacterium extorquens strains can nourish themselves using the methanol released by the stomata and release an agent promoting the growth of the seedlings of some crop plants.

  20. Stars of type MS with evidence of white dwarf companions. [IUE, Main Sequence (MS)

    Science.gov (United States)

    Peery, Benjamin F., Jr.

    1986-01-01

    A search for white dwarf companions of MS-type stars was conducted, using IUE. The overendowments of these stars in typical S-process nuclides suggest that they, like the Ba II stars, may owe their peculiar compositions to earlier mass transfer. Short-wavelength IUE spectra show striking emission line variability in HD35155, HD61913, and 4 Ori; HD35155 and 4 Ori show evidence of white dwarf companions.

  1. SWATH Mass Spectrometry Performance Using Extended Peptide MS/MS Assay Libraries*

    Science.gov (United States)

    Wu, Jemma X.; Song, Xiaomin; Pascovici, Dana; Zaw, Thiri; Care, Natasha; Krisp, Christoph; Molloy, Mark P.

    2016-01-01

    The use of data-independent acquisition methods such as SWATH for mass spectrometry based proteomics is usually performed with peptide MS/MS assay libraries which enable identification and quantitation of peptide peak areas. Reference assay libraries can be generated locally through information dependent acquisition, or obtained from community data repositories for commonly studied organisms. However, there have been no studies performed to systematically evaluate how locally generated or repository-based assay libraries affect SWATH performance for proteomic studies. To undertake this analysis, we developed a software workflow, SwathXtend, which generates extended peptide assay libraries by integration with a local seed library and delivers statistical analysis of SWATH-quantitative comparisons. We designed test samples using peptides from a yeast extract spiked into peptides from human K562 cell lysates at three different ratios to simulate protein abundance change comparisons. SWATH-MS performance was assessed using local and external assay libraries of varying complexities and proteome compositions. These experiments demonstrated that local seed libraries integrated with external assay libraries achieve better performance than local assay libraries alone, in terms of the number of identified peptides and proteins and the specificity to detect differentially abundant proteins. Our findings show that the performance of extended assay libraries is influenced by the MS/MS feature similarity of the seed and external libraries, while statistical analysis using multiple testing corrections increases the statistical rigor needed when searching against large extended assay libraries. PMID:27161445

  2. Selected ion flow tube study of the reactions of H3O+ and NO+ with a series of primary alcohols in the presence of water vapour in support of selected ion flow tube mass spectrometry

    Czech Academy of Sciences Publication Activity Database

    Španěl, Patrik; Žabka, Ján; Zymak, Illia; Smith, D.

    2017-01-01

    Roč. 31, č. 5 (2017), s. 437-446 ISSN 0951-4198 R&D Projects: GA ČR GA13-28882S; GA ČR(CZ) GA14-19693S Institutional support: RVO:61388955 Keywords : trace gas-analysis * sift-ms * breath analysis * fa-sift * ptr-ms Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 1.998, year: 2016

  3. Simultaneous quantification of endogenous and exogenous plasma glucose by isotope dilution LC-MS/MS with indirect MRM of the derivative tag.

    Science.gov (United States)

    Yu, Lingling; Wen, Chao; Li, Xing; Fang, Shiqi; Yang, Lichuan; Wang, Tony; Hu, Kaifeng

    2018-03-01

    Quantification of endogenous and exogenous plasma glucose can help more comprehensively evaluate the glucose metabolic status. A ratio-based approach using isotope dilution liquid chromatography tandem mass spectrometry (ID LC-MS/MS) with indirect multiple reaction monitoring (MRM) of the derivative tag was developed to simultaneously quantify endo-/exogenous plasma glucose. Using diluted D-[ 13 C 6 ] glucose as tracer of exogenous glucose, 12 C 6 / 13 C 6 glucoses were first derivatized and then data were acquired in MRM mode. The metabolism of exogenous glucose can be tracked and the concentration ratio of endo/exo-genous glucose can be measured by calculating the endo-/exo-genous glucose concentrations from peak area ratio of specific daughter ions. Joint application of selective derivatization and MRM analysis not only improves the sensitivity but also minimizes the interference from the background of plasma, which warrants the accuracy and reproducibility. Good agreement between the theoretical and calculated concentration ratios was obtained with a linear correlation coefficient (R) of 0.9969 in the range of D-glucose from 0.5 to 20.0 mM, which covers the healthy and diabetic physiological scenarios. Satisfactory reproducibility was obtained by evaluation of the intra- and inter-day precisions with relative standard deviations (RSDs) less than 5.16%, and relative recoveries of 85.96 to 95.92% were obtained at low, medium, and high concentration, respectively. The method was successfully applied to simultaneous determination of the endo-/exogenous glucose concentration in plasma of non-diabetic and type II diabetic cynomolgus monkeys. Graphical Abstract The scheme of the proposed ratio-based approach using isotope dilution LC-MS/MS with indirect MRM of the derivative tag for simultaneous quantification of endogenous and exogenous plasma glucose.

  4. Constraining a hybrid volatility basis-set model for aging of wood-burning emissions using smog chamber experiments: a box-model study based on the VBS scheme of the CAMx model (v5.40)

    Science.gov (United States)

    Ciarelli, Giancarlo; El Haddad, Imad; Bruns, Emily; Aksoyoglu, Sebnem; Möhler, Ottmar; Baltensperger, Urs; Prévôt, André S. H.

    2017-06-01

    In this study, novel wood combustion aging experiments performed at different temperatures (263 and 288 K) in a ˜ 7 m3 smog chamber were modelled using a hybrid volatility basis set (VBS) box model, representing the emission partitioning and their oxidation against OH. We combine aerosol-chemistry box-model simulations with unprecedented measurements of non-traditional volatile organic compounds (NTVOCs) from a high-resolution proton transfer reaction mass spectrometer (PTR-MS) and with organic aerosol measurements from an aerosol mass spectrometer (AMS). Due to this, we are able to observationally constrain the amounts of different NTVOC aerosol precursors (in the model) relative to low volatility and semi-volatile primary organic material (OMsv), which is partitioned based on current published volatility distribution data. By comparing the NTVOC / OMsv ratios at different temperatures, we determine the enthalpies of vaporization of primary biomass-burning organic aerosols. Further, the developed model allows for evaluating the evolution of oxidation products of the semi-volatile and volatile precursors with aging. More than 30 000 box-model simulations were performed to retrieve the combination of parameters that best fit the observed organic aerosol mass and O : C ratios. The parameters investigated include the NTVOC reaction rates and yields as well as enthalpies of vaporization and the O : C of secondary organic aerosol surrogates. Our results suggest an average ratio of NTVOCs to the sum of non-volatile and semi-volatile organic compounds of ˜ 4.75. The mass yields of these compounds determined for a wide range of atmospherically relevant temperatures and organic aerosol (OA) concentrations were predicted to vary between 8 and 30 % after 5 h of continuous aging. Based on the reaction scheme used, reaction rates of the NTVOC mixture range from 3.0 × 10-11 to 4. 0 × 10-11 cm3 molec-1 s-1. The average enthalpy of vaporization of secondary organic aerosol

  5. Urinary Amino Acid Analysis: A Comparison of iTRAQ®-LC-MS/MS, GC-MS, and Amino Acid Analyzer

    OpenAIRE

    Kaspar, Hannelore; Dettmer, Katja; Chan, Queenie; Daniels, Scott; Nimkar, Subodh; Daviglus, Martha L.; Stamler, Jeremiah; Elliott, Paul; Oefner, Peter J.

    2009-01-01

    Urinary amino acid analysis is typically done by cation-exchange chromatography followed by post-column derivatization with ninhydrin and UV detection. This method lacks throughput and specificity. Two recently introduced stable isotope ratio mass spectrometric methods promise to overcome those shortcomings. Using two blinded sets of urine replicates and a certified amino acid standard, we compared the precision and accuracy of gas chromatography/mass spectrometry (GC-MS) and liquid chromatog...

  6. Qualitative tissue differentiation by analysing the intensity ratios of atomic emission lines using laser induced breakdown spectroscopy (LIBS): prospects for a feedback mechanism for surgical laser systems.

    Science.gov (United States)

    Kanawade, Rajesh; Mahari, Fanuel; Klämpfl, Florian; Rohde, Maximilian; Knipfer, Christian; Tangermann-Gerk, Katja; Adler, Werner; Schmidt, Michael; Stelzle, Florian

    2015-01-01

    The research work presented in this paper focuses on qualitative tissue differentiation by monitoring the intensity ratios of atomic emissions using 'Laser Induced Breakdown Spectroscopy' (LIBS) on the plasma plume created during laser tissue ablation. The background of this study is to establish a real time feedback control mechanism for clinical laser surgery systems during the laser ablation process. Ex-vivo domestic pig tissue samples (muscle, fat, nerve and skin) were used in this experiment. Atomic emission intensity ratios were analyzed to find a characteristic spectral line for each tissue. The results showed characteristic elemental emission intensity ratios for the respective tissues. The spectral lines and intensity ratios of these specific elements varied among the different tissue types. The main goal of this study is to qualitatively and precisely identify different tissue types for tissue specific laser surgery. © 2015 The Authors. Journal of Biophotonics published by WILEY-VCH Verlag.

  7. COMPARISON OF COMMERCIAL LC MS/MS COMPATIBLE DETERGENTS WITH SODIUM DEOXYCHOLATE FOR SHOTGUN PROTEOMICS

    Directory of Open Access Journals (Sweden)

    Caleb J. Porter

    2014-12-01

    Full Text Available In this study, we compared the performance of sodium deoxycholate (SDC with several commercially available LC MS/MS compatible detergents for digestion of complex proteomic mixtures. First, the parameters affecting in-solution digestion using SDC were investigated with a full factorial experimental design. Metrics explored were trypsin ratio, digestion time, and concentration of SDC. These parameters were not found to be statistically associated with total peptide identifications in the experimental space investigated. However, in terms of digestion efficiency, digestion time was highly significant (p = 0.0095 as determined by the percent of peptides identified with missed cleavages. The optimized protocol for peptide identification and throughput was used to compare the performance of SDC with various commercially available LC MS/MS compatible surfactants namely Invitrosol, RapiGest, and PPS Silent Surfactant. The detergents were found to be similar through comparisons of the total identified peptides and the hydrophobicity of recovered peptides. We found suitable recovery across a large range of SDC concentrations determined from a bicinchoninic acid (BCA assay. In a spike down experiment, no distinct differences in total number of peptide identifications were discovered when comparing PPS (Silent Surfactant and SDC for preparation of peptide samples derived from low protein amounts (< 20 µg. Combined, these results indicate that SDC is a cost effective alternative to other commonly used LC MS/MS compatible surfactants

  8. SDSS-IV MaNGA: the impact of diffuse ionized gas on emission-line ratios, interpretation of diagnostic diagrams and gas metallicity measurements

    Science.gov (United States)

    Zhang, Kai; Yan, Renbin; Bundy, Kevin; Bershady, Matthew; Haffner, L. Matthew; Walterbos, René; Maiolino, Roberto; Tremonti, Christy; Thomas, Daniel; Drory, Niv; Jones, Amy; Belfiore, Francesco; Sánchez, Sebastian F.; Diamond-Stanic, Aleksandar M.; Bizyaev, Dmitry; Nitschelm, Christian; Andrews, Brett; Brinkmann, Jon; Brownstein, Joel R.; Cheung, Edmond; Li, Cheng; Law, David R.; Roman Lopes, Alexandre; Oravetz, Daniel; Pan, Kaike; Storchi Bergmann, Thaisa; Simmons, Audrey

    2017-04-01

    Diffuse ionized gas (DIG) is prevalent in star-forming galaxies. Using a sample of 365 nearly face-on star-forming galaxies observed by Mapping Nearby Galaxies at APO, we demonstrate how DIG in star-forming galaxies impacts the measurements of emission-line ratios, hence the interpretation of diagnostic diagrams and gas-phase metallicity measurements. At fixed metallicity, DIG-dominated low ΣHα regions display enhanced [S II]/Hα, [N II]/Hα, [O II]/Hβ and [O I]/Hα. The gradients in these line ratios are determined by metallicity gradients and ΣHα. In line ratio diagnostic diagrams, contamination by DIG moves H II regions towards composite or low-ionization nuclear emission-line region (LI(N)ER)-like regions. A harder ionizing spectrum is needed to explain DIG line ratios. Leaky H II region models can only shift line ratios slightly relative to H II region models, and thus fail to explain the composite/LI(N)ER line ratios displayed by DIG. Our result favours ionization by evolved stars as a major ionization source for DIG with LI(N)ER-like emission. DIG can significantly bias the measurement of gas metallicity and metallicity gradients derived using strong-line methods. Metallicities derived using N2O2 are optimal because they exhibit the smallest bias and error. Using O3N2, R23, N2 = [N II]/Hα and N2S2Hα to derive metallicities introduces bias in the derived metallicity gradients as large as the gradient itself. The strong-line method of Blanc et al. (IZI hereafter) cannot be applied to DIG to get an accurate metallicity because it currently contains only H II region models that fail to describe the DIG.

  9. Laboratory measurement of secondary pollutant yields from ozone reaction with HVAC filters

    International Nuclear Information System (INIS)

    Destaillats, Hugo; Chen, Wenhao; Apte, Michael; Li, Nuan; Spears, Michael; Almosni, Jeremie; Zhang, Jianshun Jensen; Fisk, William J.

    2009-01-01

    We used Proton Transfer Reaction - Mass Spectrometry (PTR-MS) and conventional sampling methods to monitor and identify trace level organic pollutants formed in heterogeneous reactions between ozone and HVAC filters in real time. Experiments were carried out using a bench-scale flow tube reactor operating with dry air and humidified air (50% RH), at realistically high ozone concentrations (150 ppbv). We explored different filter media (i.e., fiberglass and cotton/polyester blends) and different particle loadings (i.e., clean filter and filters loaded with particles for 3 months at the Lawrence Berkeley National Laboratory and the Port of Oakland, CA). Detailed emission dynamics of very low levels of certain organic pollutants from filter media upon ozone exposure in the presence of moisture have been obtained and analyzed.

  10. Detection and evaluation of embedded mild steel can material into 18 Cr-oxide dispersion strengthened steel tubes by magnetic Barkhausen emission

    Science.gov (United States)

    Kishore, G. V. K.; Kumar, Anish; Rajkumar, K. V.; Purnachandra Rao, B.; Pramanik, Debabrata; Kapoor, Komal; Jha, Sanjay Kumar

    2017-12-01

    The paper presents a new methodology for detection and evaluation of mild steel (MS) can material embedded into oxide dispersion strengthened (ODS) steel tubes by magnetic Barkhausen emission (MBE) technique. The high frequency MBE measurements (125 Hz sweep frequency and 70-200 kHz analyzing frequency) are found to be very sensitive for detection of presence of MS on the surface of the ODS steel tube. However, due to a shallow depth of information from the high frequency MBE measurements, it cannot be used for evaluation of the thickness of the embedded MS. The low frequency MBE measurements (0.5 Hz sweep frequency and 2-20 kHz analyzing frequency) indicate presence of two MBE RMS voltage peaks corresponding to the MS and the ODS steel. The ratio of the two peaks changes with the thickness of the MS and hence, can be used for measurement of the thickness of the MS layer.

  11. Performance of adaptive MS-GSC with co-channel interference

    KAUST Repository

    Daghfous, Mohamed A.

    2011-06-01

    Minimum selection generalized selection combining(MS-GSC) scheme has been proposed as a generalized power-saving variant of the conventional generalized selection combining(GSC) scheme. Previous analysis of the performance of MS-GSC has focused on interference-free environments. This paper aims to investigate the performance of adaptive signal-to-noise ratio (SNR)-based MS-GSC in the presence of co-channel interference over multipath fading channels. The adaptation thresholds are selected to enhance either the spectral efficiency or power efficiency of discrete-time rectangular signaling system. New closed-form expressions for the statistics of combined signal-to-interference-plus-noise ratio (SINR) are presented, which are then used to obtain analytical formulations for various performance measures. Numerical and simulation comparisons for the performance of the adaptation scheme are provided. © 2011 IEEE.

  12. New developments in glow discharge optical emission and mass spectrometry

    International Nuclear Information System (INIS)

    Hoffmann, Volker; Dorka, Roland; Wilken, Ludger; Wetzig, Klaus

    2000-01-01

    This paper describes new developments in flow discharge optical emission (GD-OES) and mass spectrometry (GD-MS) at IFW and presents corresponding new applications (analysis of microelectronic multi-layer system by radio frequency glow discharge optical emission spectrometry (RF-GD-OES) and analysis of pure iron by a new Grimm-type GD-MS source)

  13. Uranium isotopic ratio measurements ({sup 235}U/{sup 238}U) by laser ablation high resolution inductively coupled plasma mass spectrometry for environmental radioactivity monitoring - {sup 235}U/{sup 238}U isotope ratio analysis by LA-ICP-MS-HR for environmental radioactivity monitoring

    Energy Technology Data Exchange (ETDEWEB)

    David, K.; Mokili, M.B.; Rousseau, G.; Deniau, I.; Landesman, C. [SUBATECH, Ecole des Mines de Nantes, Universite de Nantes, CNRS/IN2P3, 4 rue Alfred Kastler, 44307 Nantes cedex 3 (France)

    2014-07-01

    The protection of the aquatic and terrestrial environments from a broad range of contaminants spread by nuclear activities (nuclear plants, weapon tests or mining) require continuous monitoring of long-lives radionuclides that were released into the environment. The precise determination of uranium isotope ratios in both natural and potential contaminated samples is of primary concern for the nuclear safeguards and the control of environmental contamination. As an example, analysis of environmental samples around nuclear plants are carried out to detect the traces in the environment originating from nuclear technology activities. This study deals with the direct analysis of {sup 235}U/{sup 238}U isotope ratios in real environmental solid samples performed with laser ablation (LA)-HR-ICP-MS. A similar technique has already been reported for the analysis of biological samples or uranium oxide particles [1,2] but to our knowledge, this was never applied on real environmental samples. The high sensitivity, rapid acquisition time and low detection limits are the main advantages of high resolution ICP-MS for accurate and precise isotope ratio measurements of uranium at trace and ultra-trace levels. In addition, the use of laser ablation allows the analysis of solid samples with minimal preparation. A a consequence, this technique is very attractive for conducting rapid direct {sup 235}U/{sup 238}U isotope ratio analysis on a large set of various matrix samples likely to be encountered in environmental monitoring such as corals, soils, sands, sediments, terrestrial and marine bio-indicators. For the present study, LA-ICP-MS-HR analyses are performed using a New Wave UP213 nano-second Nd:YAG laser coupled to a Thermo Element-XR high resolution mass spectrometer. Powdered samples are compacted with an hydraulic press (5 tons) in order to obtain disk-shaped pellet (10-13 mm in diameter and 2 mm in thickness). The NIST612 reference glass is used for LA-ICP-MS-HR tuning and as

  14. Contrasting winter and summer VOC mixing ratios at a forest site in the Western Mediterranean Basin: the effect of local biogenic emissions

    Science.gov (United States)

    Seco, R.; Peñuelas, J.; Filella, I.; Llusià, J.; Molowny-Horas, R.; Schallhart, S.; Metzger, A.; Müller, M.; Hansel, A.

    2011-12-01

    Atmospheric volatile organic compounds (VOCs) are involved in ozone and aerosol generation, thus having implications for air quality and climate. VOCs and their emissions by vegetation also have important ecological roles as they can protect plants from stresses and act as communication cues between plants and between plants and animals. In spite of these key environmental and biological roles, the reports on seasonal and daily VOC mixing ratios in the literature for Mediterranean natural environments are scarce. We conducted seasonal (winter and summer) measurements of VOC mixing ratios in an elevated (720 m a.s.l.) holm oak Mediterranean forest site near the metropolitan area of Barcelona (NE Iberian Peninsula). Methanol was the most abundant compound among all the VOCs measured in both seasons. While aromatic VOCs showed almost no seasonal variability, short-chain oxygenated VOCs presented higher mixing ratios in summer, presumably due to greater emission by vegetation and increased photochemistry, both enhanced by the high temperatures and solar radiation in summer. Isoprenoid VOCs showed the biggest seasonal change in mixing ratios: they increased by one order of magnitude in summer, as a result of the vegetation's greater physiological activity and emission rates. The maximum diurnal concentrations of ozone increased in summer too, most likely due to more intense photochemical activity and the higher levels of VOCs in the air. The daily variation of VOC mixing ratios was mainly governed by the wind regime of the mountain, as the majority of the VOC species analyzed followed a very similar diel cycle. Mountain and sea breezes that develop after sunrise advect polluted air masses to the mountain. These polluted air masses had previously passed over the urban and industrial areas surrounding the Barcelona metropolitan area, where they were enriched in NOx and in VOCs of biotic and abiotic origin. Moreover, these polluted air masses receive additional biogenic

  15. Emission factor ratios, SOA mass yields, and the impact of vehicular emissions on SOA formation

    Science.gov (United States)

    Ensberg, J. J.; Hayes, P. L.; Jimenez, J. L.; Gilman, J. B.; Kuster, W. C.; de Gouw, J. A.; Holloway, J. S.; Gordon, T. D.; Jathar, S.; Robinson, A. L.; Seinfeld, J. H.

    2014-03-01

    The underprediction of ambient secondary organic aerosol (SOA) levels by current atmospheric models in urban areas is well established, yet the cause of this underprediction remains elusive. Likewise, the relative contribution of emissions from gasoline- and diesel-fueled vehicles to the formation of SOA is generally unresolved. We investigate the source of these two discrepancies using data from the 2010 CalNex experiment carried out in the Los Angeles Basin (Ryerson et al., 2013). Specifically, we use gas-phase organic mass (GPOM) and CO emission factors in conjunction with measured enhancements in oxygenated organic aerosol (OOA) relative to CO to quantify the significant lack of closure between expected and observed organic aerosol concentrations attributable to fossil-fuel emissions. Two possible conclusions emerge from the analysis to yield consistency with the ambient data: (1) vehicular emissions are not a dominant source of anthropogenic fossil SOA in the Los Angeles Basin, or (2) the ambient SOA mass yields used to determine the SOA formation potential of vehicular emissions are substantially higher than those derived from laboratory chamber studies.

  16. Secondary organic aerosol formation from road vehicle emissions

    Science.gov (United States)

    Pieber, Simone M.; Platt, Stephen M.; El Haddad, Imad; Zardini, Alessandro A.; Suarez-Bertoa, Ricardo; Slowik, Jay G.; Huang, Ru-Jin; Hellebust, Stig; Temime-Roussel, Brice; Marchand, Nicolas; Drinovec, Luca; Mocnik, Grisa; Baltensperger, Urs; Astorga, Covadogna; Prévôt, André S. H.

    2014-05-01

    Organic aerosol particles (OA) are a major fraction of the submicron particulate matter. OA consists of directly emitted primary (POA) and secondary OA (SOA). SOA is formed in-situ in the atmosphere via the reaction of volatile organic precursors. The partitioning of SOA species depends not only on the exposure to oxidants, but for instance also on temperature, relative humidity (RH), and the absorptive mass chemical composition (presence of inorganics) and concentration. Vehicle exhaust is a known source of POA and likely contributes to SOA formation in urban areas [1;2]. This has recently been estimated by (i) analyzing ambient data from urban areas combined with fuel consumption data [3], (ii) by examining the chemical composition of raw fuels [4], or (iii) smog chamber studies [5, 6]. Contradictory and thus somewhat controversial results in the relative quantity of SOA from diesel vs. gasoline vehicle exhaust were observed. In order to elucidate the impact of variable ambient conditions on the potential SOA formation of vehicle exhaust, and its relation to the emitted gas phase species, we studied SOA formed from the exhaust of passenger cars and trucks as a function of fuel and engine type (gasoline, diesel) at different temperatures (T 22 vs. -7oC) and RH (40 vs. 90%), as well as with different levels of inorganic salt concentrations. The exhaust was sampled at the tailpipe during regulatory driving cycles on chassis dynamometers, diluted (200 - 400x) and introduced into the PSI mobile smog chamber [6], where the emissions were subjected to simulated atmospheric ageing. Particle phase instruments (HR-ToF-AMS, aethalometers, CPC, SMPS) and gas phase instruments (PTR-TOF-MS, CO, CO2, CH4, THC, NH3 and other gases) were used online during the experiments. We found that gasoline emissions, because of cold starts, were generally larger than diesel, especially during cold temperatures driving cycles. Gasoline vehicles also showed the highest SOA formation

  17. Compositional Signatures of Conventional, Free Range, and Organic Pork Meat Using Fingerprint Techniques

    Directory of Open Access Journals (Sweden)

    Gislene B. Oliveira

    2015-08-01

    Full Text Available Consumers’ interest in the way meat is produced is increasing in Europe. The resulting free range and organic meat products retail at a higher price, but are difficult to differentiate from their counterparts. To ascertain authenticity and prevent fraud, relevant markers need to be identified and new analytical methodology developed. The objective of this pilot study was to characterize pork belly meats of different animal welfare classes by their fatty acid (Fatty Acid Methyl Ester—FAME, non-volatile compound (electrospray ionization-tandem mass spectrometry—ESI-MS/MS, and volatile compound (proton-transfer-reaction mass spectrometry—PTR-MS fingerprints. Well-defined pork belly meat samples (13 conventional, 15 free range, and 13 organic originating from the Netherlands were subjected to analysis. Fingerprints appeared to be specific for the three categories, and resulted in 100%, 95.3%, and 95.3% correct identity predictions of training set samples for FAME, ESI-MS/MS, and PTR-MS respectively and slightly lower scores for the validation set. Organic meat was also well discriminated from the other two categories with 100% success rates for the training set for all three analytical approaches. Ten out of 25 FAs showed significant differences in abundance between organic meat and the other categories, free range meat differed significantly for 6 out of the 25 FAs. Overall, FAME fingerprinting presented highest discrimination power.

  18. Compositional Signatures of Conventional, Free Range, and Organic Pork Meat Using Fingerprint Techniques.

    Science.gov (United States)

    Oliveira, Gislene B; Alewijn, Martin; Boerrigter-Eenling, Rita; van Ruth, Saskia M

    2015-08-25

    Consumers' interest in the way meat is produced is increasing in Europe. The resulting free range and organic meat products retail at a higher price, but are difficult to differentiate from their counterparts. To ascertain authenticity and prevent fraud, relevant markers need to be identified and new analytical methodology developed. The objective of this pilot study was to characterize pork belly meats of different animal welfare classes by their fatty acid (Fatty Acid Methyl Ester-FAME), non-volatile compound (electrospray ionization-tandem mass spectrometry-ESI-MS/MS), and volatile compound (proton-transfer-reaction mass spectrometry-PTR-MS) fingerprints. Well-defined pork belly meat samples (13 conventional, 15 free range, and 13 organic) originating from the Netherlands were subjected to analysis. Fingerprints appeared to be specific for the three categories, and resulted in 100%, 95.3%, and 95.3% correct identity predictions of training set samples for FAME, ESI-MS/MS, and PTR-MS respectively and slightly lower scores for the validation set. Organic meat was also well discriminated from the other two categories with 100% success rates for the training set for all three analytical approaches. Ten out of 25 FAs showed significant differences in abundance between organic meat and the other categories, free range meat differed significantly for 6 out of the 25 FAs. Overall, FAME fingerprinting presented highest discrimination power.

  19. Application of ICP-MS in Environmental Sampling Analysis for Safeguards

    International Nuclear Information System (INIS)

    Eko Pudjadi; Petrus Zacharias; Budi Prayitno

    2004-01-01

    Environmental samples measured by ICP-MS were analyzed for safeguards. There are two isotopes in environmental sampling that is used to find out the origin of nuclear materials and verify undeclared nuclear activities. Uranium isotopes are 234 U, 235 U, 236 U and 238 U and Plutonium isotopes are 239 Pu, 240 Pu, 241 Pu and 242 Pu. Uranium isotopes are used to verify an existing of nuclear power plants, enrichment plants or reprocessing plants. Plutonium isotopes are used to clarify global fallout from nuclear weapon testing and accident of nuclear facility or military purposes. The high sensitivity of ICP-MS can detect the isotopic fingerprint and trace elements in ppb concentration; ICP-MS has been applied to measure 235 U isotopic ratio and 240 Pu/ 239 Pu isotopic ratios. The sensitivity of ICP-MS is high precision and low operational cost in environmental sampling and can be considered in nuclear power design based on safeguards for development countries. (author)

  20. Geographical provenancing of purple grape juices from different farming systems by proton transfer reaction mass spectrometry using supervised statistical techniques

    NARCIS (Netherlands)

    Granato, Daniel; Koot, Alex; Ruth, van S.M.

    2015-01-01

    BACKGROUND: Organic, biodynamic and conventional purple grape juices (PGJ; n = 79) produced in Brazil and Europe were characterized by volatile organic compounds (m/z 20-160) measured by proton transfer reaction mass spectrometry (PTR-MS), and classification models were built using supervised

  1. Natural gas facility methane emissions: measurements by tracer flux ratio in two US natural gas producing basins

    Directory of Open Access Journals (Sweden)

    Tara I. Yacovitch

    2017-11-01

    Full Text Available Methane (CH4 emission rates from a sample of natural gas facilities across industry sectors were quantified using the dual tracer flux ratio methodology. Measurements were conducted in study areas within the Fayetteville shale play, Arkansas (FV, Sept–Oct 2015, 53 facilities, and the Denver-Julesburg basin, Colorado, (DJ, Nov 2014, 21 facilities. Distributions of methane emission rates at facilities by type are computed and statistically compared with results that cover broader geographic regions in the US (Allen et al., 2013, Mitchell et al., 2015. DJ gathering station emission rates (kg CH4 hr–1 are lower, while FV gathering and production sites are statistically indistinguishable as compared to these multi-basin results. However, FV gathering station throughput-normalized emissions are statistically lower than multi-basin results (0.19% vs. 0.44%. This implies that the FV gathering sector is emitting less per unit of gas throughput than would be expected from the multi-basin distribution alone. The most common emission rate (i.e. mode of the distribution for facilities in this study is 40 kg CH4 hr–1 for FV gathering stations, 1.0 kg CH4 hr–1 for FV production pads, and 11 kg CH4 hr–1 for DJ gathering stations. The importance of study design is discussed, including the benefits of site access and data sharing with industry and of a scientist dedicated to measurement coordination and site choice under evolving wind conditions.

  2. Variations in the Gender Ratio of Multiple Sclerosis Linked to Converging Smoking Trends in Men and Women

    DEFF Research Database (Denmark)

    Palacios, Natalia; Alonso, Alvaro; Brønnum-Hansen, Henrik

    2010-01-01

    -dependent relationship exists between changing female-to male ratios of smoking and Multiple Sclerosis (MS) in worldwide birth cohorts from previously published studies. BACKGROUND: Smoking behavior in industrialized nations has changed dramatically over the second half of the 20th century, with diverging patterns...... in male and female smoking rates. During the same time period, an increase in the female to male ratio in MS incidence has been reported. We examined whether MS incidence in the two genders changed concomitantly with smoking, as would be expected if smoking truly increased MS risk. DESIGN/METHODS: We...... identified relevant studies reporting male and female age-specific incidence of MS throughout the world using within-country birth cohorts as units of observation. For each country and birth cohort, we then estimated the male to female ratio in MS incidence, and correlated these ratios with the corresponding...

  3. One-Dimensional-Ratio Measures of Atrophy Progression in Multiple Sclerosis as Evaluated by Longitudinal Magnetic Resonance Imaging

    International Nuclear Information System (INIS)

    Martola, J.; Wiberg Kristoffersen, M.; Aspelin, P.; Stawiarz, L.; Fredrikson, S.; Hillert, J.; Bergstroem, J.; Flodmark, O.

    2009-01-01

    Background: For decades, normalized one-dimensional (1D) measures have been used in the evaluation of brain atrophy. In multiple sclerosis (MS), the use of normalized linear measures over longitudinal follow-up remains insufficiently documented. Purpose: To evaluate the association between different regional atrophy measures and disability in MS patients over four decades in a longitudinal cross-sectional study. Material and Methods: 37 consecutively selected MS patients were included. At baseline, patients had a range of disease duration (1-33 years) and age (24-65 years). Each patient was followed by magnetic resonance imaging (MRI) for a mean of 9.25 years (range 7.3-10 years). Four 1D measures were applied at three time points on axial 5-mm T1-weighted images. Three clinical MS subgroups were represented: relapsing-remitting MS (RRMS), secondary progressive MS (SPMS), and primary progressive MS (PPMS). Results: There were significant changes in all 1D ratios during follow-up. The Evans ratio (ER) and the bifrontal ratio (BFR) were associated with the development of disability. Changes of ER and BFR reflected more aggressive disease progression, as expressed by MS severity score (MSSS). Conclusion: All four normalized ratios showed uniform atrophy progression, suggesting a consistent rate of atrophy over long-term disease duration independent of MS course. Disability status correlated with 1D measures, suggesting that serial evaluation of Evans and bifrontal ratios might contribute to the radiological evaluation of MS patients

  4. ICP-MS/MS-Based Ionomics: A Validated Methodology to Investigate the Biological Variability of the Human Ionome.

    Science.gov (United States)

    Konz, Tobias; Migliavacca, Eugenia; Dayon, Loïc; Bowman, Gene; Oikonomidi, Aikaterini; Popp, Julius; Rezzi, Serge

    2017-05-05

    We here describe the development, validation and application of a quantitative methodology for the simultaneous determination of 29 elements in human serum using state-of-the-art inductively coupled plasma triple quadrupole mass spectrometry (ICP-MS/MS). This new methodology offers high-throughput elemental profiling using simple dilution of minimal quantity of serum samples. We report the outcomes of the validation procedure including limits of detection/quantification, linearity of calibration curves, precision, recovery and measurement uncertainty. ICP-MS/MS-based ionomics was used to analyze human serum of 120 older adults. Following a metabolomic data mining approach, the generated ionome profiles were subjected to principal component analysis revealing gender and age-specific differences. The ionome of female individuals was marked by higher levels of calcium, phosphorus, copper and copper to zinc ratio, while iron concentration was lower with respect to male subjects. Age was associated with lower concentrations of zinc. These findings were complemented with additional readouts to interpret micronutrient status including ceruloplasmin, ferritin and inorganic phosphate. Our data supports a gender-specific compartmentalization of the ionome that may reflect different bone remodelling in female individuals. Our ICP-MS/MS methodology enriches the panel of validated "Omics" approaches to study molecular relationships between the exposome and the ionome in relation with nutrition and health.

  5. Contrasting winter and summer VOC mixing ratios at a forest site in the Western Mediterranean Basin: the effect of local biogenic emissions

    Directory of Open Access Journals (Sweden)

    R. Seco

    2011-12-01

    Full Text Available Atmospheric volatile organic compounds (VOCs are involved in ozone and aerosol generation, thus having implications for air quality and climate. VOCs and their emissions by vegetation also have important ecological roles as they can protect plants from stresses and act as communication cues between plants and between plants and animals. In spite of these key environmental and biological roles, the reports on seasonal and daily VOC mixing ratios in the literature for Mediterranean natural environments are scarce.

    We conducted seasonal (winter and summer measurements of VOC mixing ratios in an elevated (720 m a.s.l. holm oak Mediterranean forest site near the metropolitan area of Barcelona (NE Iberian Peninsula. Methanol was the most abundant compound among all the VOCs measured in both seasons. While aromatic VOCs showed almost no seasonal variability, short-chain oxygenated VOCs presented higher mixing ratios in summer, presumably due to greater emission by vegetation and increased photochemistry, both enhanced by the high temperatures and solar radiation in summer. Isoprenoid VOCs showed the biggest seasonal change in mixing ratios: they increased by one order of magnitude in summer, as a result of the vegetation's greater physiological activity and emission rates. The maximum diurnal concentrations of ozone increased in summer too, most likely due to more intense photochemical activity and the higher levels of VOCs in the air.

    The daily variation of VOC mixing ratios was mainly governed by the wind regime of the mountain, as the majority of the VOC species analyzed followed a very similar diel cycle. Mountain and sea breezes that develop after sunrise advect polluted air masses to the mountain. These polluted air masses had previously passed over the urban and industrial areas surrounding the Barcelona metropolitan area, where they were enriched in NOx and in VOCs of biotic and abiotic origin. Moreover, these

  6. Proton transfer reaction-mass spectrometry volatile organic compound fingerprinting for monovarietal extra virgin olive oil identification

    NARCIS (Netherlands)

    Ruiz-Samblas, C.; Tres, A.; Koot, A.H.; Ruth, van S.M.; Gonzalez-Casado, A.; Cuadros-Rodriguez, L.

    2012-01-01

    Proton transfer reaction-mass spectrometry (PTR-MS) is a relatively new technique that allows the fast and accurate qualification of the volatile organic compound (VOC) fingerprint. This paper describes the analysis of thirty samples of extra virgin olive oil, of five different varieties of olive

  7. Comparison between proton transfer reaction mass spectrometry and near infrared spectroscopy for the authentication of Brazilian coffee

    NARCIS (Netherlands)

    Monteiro, Pablo Inocêncio; Santos, Jânio Sousa; Alvarenga Brizola, Vitor Rafael; Pasini Deolindo, Carolina Turnes; Koot, Alex; Boerrigter-Eenling, Rita; Ruth, van Saskia; Georgouli, Konstantia; Koidis, Anastasios; Granato, Daniel

    2018-01-01

    In this study, proton-transfer reaction mass spectrometry (PTR-MS) and near-infrared spectroscopy (NIRS) were compared for the authentication of geographical and farming system origins of Brazilian coffees. For this purpose, n = 19 organic (ORG) and n = 26 conventional (CONV) coffees from

  8. Products of Ozone-Initiated Chemistry in a Simulated Aircraft Environment

    DEFF Research Database (Denmark)

    Wisthaler, Armin; Tamás, Gyöngyi; Wyon, David P.

    2005-01-01

    We used proton-transfer-reaction mass spectrometry (PTR-MS) to examine the products formed when ozone reacted with the materials in a simulated aircraft cabin, including a loaded high-efficiency particulate air (HEPA) filter in the return air system. Four conditions were examined: cabin (baseline...

  9. VOCs monitoring of new materials for ceramic tiles decoration: GC–MS analysis of emissions from common vehicles and inkjet inks during firing in laboratory

    International Nuclear Information System (INIS)

    Ferrari, G.; Zannini, P.

    2017-01-01

    The decoration of ceramic tiles “ink-jet revolution” has brought significant advantages to tiles manufacturing, but the explosive diffusion, until 4–5 years ago, of this technique has not been accomplished by an adequate scientific research. Among all the features that have to be studied yet, one of the most important is the influence of the new generation inks on the total emission at ceramic chimneys. In this paper, we present a first characterization of emissions from a set of commercial inks and vehicles: they were collected by propter firing of samples in an electric kiln and analyzed by GC–MS. This study is part of a larger research project, which includes the chemical characterization and the evaluation of thermal behavior of inks and vehicles by TG-DTA and other techniques. The obtained results permit to divide common vehicles into 3 classes, depending on their thermal behavior and emissions pattern. Inks, most of which present an ester based formulation, sometimes mixed with glycols or paraffins, follow the behavior of their single components. The most common formulation leads to the presence in the emission pattern of evaporation products (2-ethylhexyl esters of lauric, myristic, decanoic and octanoic acids) and decomposition products (mainly aldehydes and 2-ethyl-1-hexanol). [es

  10. VOCs monitoring of new materials for ceramic tiles decoration: GC–MS analysis of emissions from common vehicles and inkjet inks during firing in laboratory

    Directory of Open Access Journals (Sweden)

    Giorgia Ferrari

    2017-09-01

    Full Text Available The decoration of ceramic tiles “ink-jet revolution” has brought significant advantages to tiles manufacturing, but the explosive diffusion, until 4–5 years ago, of this technique has not been accomplished by an adequate scientific research. Among all the features that have to be studied yet, one of the most important is the influence of the new generation inks on the total emission at ceramic chimneys. In this paper, we present a first characterization of emissions from a set of commercial inks and vehicles: they were collected by propter firing of samples in an electric kiln and analyzed by GC–MS. This study is part of a larger research project, which includes the chemical characterization and the evaluation of thermal behavior of inks and vehicles by TG-DTA and other techniques. The obtained results permit to divide common vehicles into 3 classes, depending on their thermal behavior and emissions pattern. Inks, most of which present an ester based formulation, sometimes mixed with glycols or paraffins, follow the behavior of their single components. The most common formulation leads to the presence in the emission pattern of evaporation products (2-ethylhexyl esters of lauric, myristic, decanoic and octanoic acids and decomposition products (mainly aldehydes and 2-ethyl-1-hexanol.

  11. Identification of alkyl dimethylbenzylammonium surfactants in water samples by solid-phase extraction followed by ion trap LC/MS and LC/MS/MS

    Science.gov (United States)

    Ferrer, I.; Furlong, E.T.

    2001-01-01

    A novel methodology was developed for the determination of alkyl (C12, C14, and C16) dimethylbenzylammonium chloride (benzalkonium chloride or BAC, Chemical Abstract Service number: 8001-54-5) in water samples. This method is based on solid-phase extraction (SPE) using polymeric cartridges, followed by high-performance liquid chromatography/ion trap mass spectrometry (LC/MS) and tandem mass spectrometry(MS/MS) detection, equipped with an electrospray interface in positive ion mode. Chromatographic separation was achieved for three BAC homologues by using a C18 column and a gradient of acetonitrile/10 millimolar aqueous ammonium formate. Total method recoveries were higher than 71% in different water matrices. The main ions observed by LC/MS were at mass-to-charge ratios (m/z) of 304, 332, and 360, which correspond to the molecular ions of the C12, C14, and C16 alkyl BAC, respectively. The unequivocal structural identification of these compounds in water samples was performed by LC/MS/MS after isolation and subsequent fragmentation of each molecular ion. The main fragmentation observed for the three different homologues corresponded to the loss of the toluyl group in the chemical structure, which leads to the fragment ions at m/z 212, 240, and 268 and a tropylium ion, characteristic of all homologues, at m/z 91. Detection limits for the methodology developed in this work were in the low nanogram-per-liter range. Concentration levels of BAC - ranging from 1.2 to 36.6 micrograms per liter - were found in surface-water samples collected downstream from different wastewater-treatment discharges, thus indicating its input and persistence through the wastewater-treatment process.

  12. Storm/Quiet Ratio Comparisons Between TIMED/SABER NO (sup +)(v) Volume Emission Rates and Incoherent Scatter Radar Electron Densities at E-Region Altitudes

    Science.gov (United States)

    Fernandez, J. R.; Mertens, C. J.; Bilitza, D.; Xu, X.; Russell, J. M., III; Mlynczak, M. G.

    2009-01-01

    Broadband infrared limb emission at 4.3 microns is measured by the TIMED/SABER instrument. At night, these emission observations at E-region altitudes are used to derive the so called NO+(v) Volume Emission Rate (VER). NO+(v) VER can be derived by removing the background CO2(v3) 4.3 microns radiance contribution using SABER-based non-LTE radiation transfer models, and by performing a standard Abel inversion on the residual radiance. SABER observations show that NO+(v) VER is significantly enhanced during magnetic storms in accordance with increased ionization of the neutral atmosphere by auroral electron precipitation, followed by vibrational excitation of NO+ (i.e., NO+(v)) from fast exothermic ion-neutral reactions, and prompt infrared emission at 4.3 m. Due to charge neutrality, the NO+(v) VER enhancements are highly correlated with electron density enhancements, as observed for example by Incoherent Scatter Radar (ISR). In order to characterize the response of the storm-time E-region from both SABER and ISR measurements, a Storm/Quiet ratio (SQR) quantity is defined as a function of altitude. For SABER, the SQR is the ratio of the storm-to-quiet NO+(v) VER. SQR is the storm-to-quiet ratio of electron densities for ISR. In this work, we compare SABER and ISR SQR values between 100 to 120 km. Results indicate good agreement between these measurements. SQR values are intended to be used as a correction factor to be included in an empirical storm-time correction to the International Reference Ionosphere model at E-region altitudes.

  13. Determination of trace element concentrations and stable lead, uranium and thorium isotope ratios by quadrupole-ICP-MS in NORM and NORM-polluted sample leachates

    International Nuclear Information System (INIS)

    Mas, J.L.; Villa, M.; Hurtado, S.; García-Tenorio, R.

    2012-01-01

    Highlights: ► Polluted sediment and NORM samples. ► An efficient yet fast process allowing multi-parametric determinations in 206 Pb/ 207 Pb/ 208 Pb, 238 U/ 234 U and 232 Th/ 230 Th isotope ratios using a single sample aliquot and a single instrument (ICP-QMS). Eichrom UTEVA ® extraction chromatography minicolumns were used to separate uranium and thorium in sample leachates. Independent ICP-MS determinations of uranium and thorium isotope ratios were carried out afterwards. Previously a small aliquot of the leachate was used for the determination of trace element concentrations and lead isotope ratios. Several radiochemical arrangements were tested to get maximum performances and simplicity of the method. The performances of the method were studied in terms of chemical yields of uranium and thorium and removal of the potentially interfering elements. The established method was applied to samples from a chemical industry and sediments collected in a NORM-polluted scenario. The results obtained from our method allowed us to infer not only the extent, but also the sources of the contamination in the area.

  14. 87Sr/86Sr isotope ratio analysis by laser ablation MC-ICP-MS in scales, spines, and fin rays as a nonlethal alternative to otoliths for reconstructing fish life history

    Science.gov (United States)

    Willmes, Malte; Glessner, Justin J. G.; Carleton, Scott A.; Gerrity, Paul C.; Hobbs, James A.

    2016-01-01

    Strontium isotope ratios (87Sr/86Sr) in otoliths are a well-established tool to determine origins and movement patterns of fish. However, otolith extraction requires sacrificing fish, and when working with protected or endangered species, the use of nonlethal samples such as scales, spines, and fin rays is preferred. Unlike otoliths that are predominantly aragonite, these tissues are composed of biological apatite. Laser ablation multicollector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) analysis of biological apatite can induce significant interference on mass 87, causing inaccurate 87Sr/86Sr measurements. To quantify this interference, we applied LA-MC-ICP-MS to three marine samples (white seabass (Atractoscion nobilis) otolith; green sturgeon (Acipenser medirostris) pectoral fin ray; salmon shark (Lamna ditropis) tooth), and freshwater walleye (Sander vitreus) otoliths, scales, and spines). Instrument conditions that maximize signal intensity resulted in elevated 87Sr/86Sr isotope ratios in the bioapatite samples, related to a polyatomic interference (40Ca31P16O, 40Ar31P16O). Retuning instrument conditions to reduce oxide levels removed this interference, resulting in accurate 87Sr/86Sr ratios across all tissue samples. This method provides a novel, nonlethal alternative to otolith analysis to reconstruct fish life histories.

  15. Multielement determination and speciation of major-to-ultratrace elements in green tea leaves by ICP-AES and ICP-MS

    International Nuclear Information System (INIS)

    Matsuura, Hirotaka; Hokura, Akiko; Haraguchi, Hiroki

    2000-01-01

    In order to investigate the multi-elemental composition of green tea leaves as well as chemical species in tea infusions, inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS) were used for elemental analysis and elemental speciation with the aid of size exclusion chromatography (SEC). As a result, the multielement determination of major-to-ultratrace elements in green tea leaves and green tea infusions was carried out by ICP-AES and ICP-MS. About 40 elements in these tea samples could be determined in a wide concentration range of over 8 orders of magnitude. The extraction efficiency of each element was estimated as the ratio of its concentration in tea infusion to that in tea leaves. It was found from the experimental results that the elements in tea leaves could be classified into three characteristic groups, depending on their extraction efficiencies. Furthermore, tea infusions were analyzed by a combined system of SEC, UV absorption detector, and ICP-AES (or ICP-MS) for the speciation of major-to-ultratrace elements. Most of the elements in tea infusions were found to be present as associated complexes with large organic molecules. (author)

  16. Dating of Uranium Materials by Using Combination of ICP-MS and SIMS

    International Nuclear Information System (INIS)

    Stebelkov, Y.; Aleshin, M.; Elantyev, I.; Grachev, A.; Zhizhin, K.; Stebelkov, V.

    2015-01-01

    The age of nuclear and some other radioactive materials can be determined undoubtedly by using ICP-MS techniques. But it can be correct if only one nuclear or another radioactive material is presented in analyzed sample and no isotope-chronograph presented in background particles in significant quantities. For particle analysis, which can be implemented by using SIMS, these restrictions are not valid. Practically one particle always characterizes only one material and does not contain background isotopes-chronographs. But age determination is based on the result of measuring of the content ratio of Th230 and U234. The difference of ionization coefficients of uranium and thorium and dependence of these coefficients on composition of particle does not allow using this method directly for age determination. Nevertheless SIMS is useful for dating of uranium materials, especially if the sample can contain small amounts of different materials. In this case the analysis of different fragments of materials by SIMS can confirm or not confirm the result, had been obtained by ICP-MS. If all detected and analyzed particles and fragments will have the same ratio of ion currents of Th230 and U234, the result of ICP-MS is true. If particles and fragments will have different ratios the result of ICP-MS cannot be related to any of presented materials. But in the last case the ages of different materials can be still estimated if different fragments have different ages, but the same elemental composition. The ''age'' had been determined by ICP-MS can be correlated with the average ratio of ion currents of Th230 and U234 had been determined by SIMS for all analyzed particles or fragments. This correlation determines the ratio of ionization coefficients of uranium and thorium, which should be the same for particles with the same elemental composition. (author)

  17. Aromatic and proteomic analyses corroborate the distinction between Mediterranean landraces and modern varieties of durum wheat

    Czech Academy of Sciences Publication Activity Database

    Federico, V.; Pompeiano, Antonio; Gu, Z.; Lo Presti, E.; Whitney, L.; Monti, M.; Di Miceli, G.; Giambalvo, D.; Ruisi, P.; Guglielminetti, L.; Mancuso, S.

    2016-01-01

    Roč. 6, oct (2016), č. článku 34619. ISSN 2045-2322 Institutional support: RVO:67179843 Keywords : PTR-TOF-MS * volatile compounds * gluten strength * rapid characterization * protein-composition * extrusion-cooking * quality * cultivars * flour * subunits Subject RIV: GC - Agronomy Impact factor: 4.259, year: 2016

  18. Almahata Sitta MS-MU-011 and MS-MU-012: Formation Conditions of Two Unusual Rocks From the Ureilite Parent Body

    Science.gov (United States)

    Mikouchi, T.; Takenouchi, A.; Zolensky, M. E.; Hoffmann, V. H.

    2018-01-01

    Almahata Sitta meteorites are unique polymict breccia, comprising of many different meteorite groups as individual fragments dominated by ureilite lithologies and are considered to be recovered fragments of the asteroid 2008TC3. Recently, two unusual Almahata Sitta samples (MS-MU-011 and MS-MU-012) have been reported that show close petrogenetic relationships to ureilites. MS-MU-011 is a trachyandesite mainly composed of feldspar (plagioclase and anorthoclase) and pyroxene (pigeonite and augite) having ureilitic oxygen isotopic ratios. MS-MU-012 is the first ureilite example (unbrecciated) containing primary plagioclase crystals. The findings of these two rock types are important to better understand formation conditions of ureilites and the evolution of their parent body(s). In this abstract we discuss formation conditions of these ureilite-related rocks using redox state estimate by Fe valence states of plagioclase and olivine cooling rate calculations.

  19. Effects of carbon sources and COD/N ratio on N2O emissions in subsurface flow constructed wetlands.

    Science.gov (United States)

    Lyu, Wanlin; Huang, Lei; Xiao, Guangquan; Chen, Yucheng

    2017-12-01

    A set of constructed wetlands under two different carbon sources, namely, glucose (CW) and sodium acetate (YW), was established at a laboratory scale with influent COD/N ratios of 20:1, 10:1, 7:1, 4:1, and 0 to analyze the influence of carbon supply on nitrous oxide emissions. Results showed that the glucose systems generated higher N 2 O emissions than those of the sodium acetate systems. The higher amount of N 2 O-releasing fluxes in the CWs than in the YWs was consistent with the higher NO 2 - -N accumulation in the former than in the latter. Moreover, electron competition was tighter in the CWs and contributed to the incomplete denitrification with poor N 2 O production performance. Illumina MiSeq sequencing demonstrated that some denitrifying bacteria, such as Denitratisoma, Bacillus, and Zoogloea, were higher in the YWs than in the CWs. This result indicated that the carbon source is important in controlling N 2 O emissions in microbial communities. Copyright © 2017. Published by Elsevier Ltd.

  20. Theoretical calculations of L alpha one x-ray emission intensity ratios for uranium in various matrices: a comparison with experimental values

    International Nuclear Information System (INIS)

    Anderson, L.D.

    1976-01-01

    The U L/sub α1/ x-ray emission intensity ratios (I/sub lambda/sub L//I sub lambda/sub L/, sub 100 percent/sub UO 2 /) in various matrices were calculated using the fundamental parameters formula of Criss and Birks and mass absorption coefficients calculated from a formula developed by Dewey. The use of the intensity ratio made it unnecessary to know the fluorescence yield for the U L/sub III/ level, the probability of emission of the U L/sub α1/ line, and the jump ratios for the three absorption edges of uranium. Also, since an intensity ratio was used, the results are independent of the x-ray tube current and the spectral distribution of the x-ray tube. A method is presented to calculate the intensity ratios for x-ray tube voltages other than the value (45 kV) used in the calculations. The theoretical results are calculated and compared with the experimental results obtained for 141 matrices. Difficulties due to oxidation of some of the metal powders used in the sample preparation, to small concentrations of uranium, and to an excessively large number of elements present in some of the samples resulted in the invalidation of the experimental results for 91 of the matrices. For the remaining 50 matrices, the theoretical and experimental values agreed to within +-5 percent relative error for 36 matrices; to within +-5 percent to +- 10 percent for 7 matrices; to within +-10 percent to +-20 percent for 6 matrices; and was greater than +-20 percent for 1 matrix

  1. Volcanic SO2 and SiF4 visualization using 2-D thermal emission spectroscopy – Part 1: Slant-columns and their ratios

    Directory of Open Access Journals (Sweden)

    M. Grutter

    2012-02-01

    Full Text Available The composition and emission rates of volcanic gas plumes provide insight of the geologic internal activity, atmospheric chemistry, aerosol formation and radiative processes around it. Observations are necessary for public security and the aviation industry. Ground-based thermal emission infrared spectroscopy, which uses the radiation of the volcanic gas itself, allows for continuously monitoring during day and night from a safe distance. We present measurements on Popocatépetl volcano based on thermal emission spectroscopy during different campaigns between 2006–2009 using a Scanning Infrared Gas Imaging System (SIGIS. The experimental set-up, measurement geometries and analytical algorithms are described. The equipment was operated from a safe distance of 12 km from the volcano at two different spectral resolutions: 0.5 and 4 cm−1. The 2-dimensional scanning capability of the instrument allows for an on-line visualization of the volcanic SO2 plume and its animation. SiF4 was also identified in the infrared spectra recorded at both resolutions. The SiF4/SO2 molecular ratio can be calculated from each image and used as a highly useful parameter to follow changes in volcanic activity. A small Vulcanian eruption was monitored during the night of 16 to 17 November 2008 and strong ash emission together with a pronounced SO2 cloud was registered around 01:00 a.m. LST (Local Standard Time. Enhanced SiF4/SO2 ratios were observed before and after the eruption. A validation of the results from thermal emission measurements with those from absorption spectra of the moon taken at the same time, as well as an error analysis, are presented. The inferred propagation speed from sequential images is used in a subsequent paper (Part 2 to calculate the emission rates at different distances from the crater.

  2. Lyman alpha emission in nearby star-forming galaxies with the lowest metallicities and the highest [OIII]/[OII] ratios

    Science.gov (United States)

    Izotov, Yuri

    2017-08-01

    The Lyman alpha line of hydrogen is the strongest emission line in galaxies and the tool of predilection for identifying and studying star-forming galaxies over a wide range of redshifts, especially in the early universe. However, it has become clear over the years that not all of the Lyman alpha radiation escapes, due to its resonant scattering on the interstellar and intergalactic medium, and absorption by dust. Although our knowledge of the high-z universe depends crucially on that line, we still do not have a complete understanding of the mechanisms behind the production, radiative transfer and escape of Lyman alpha in galaxies. We wish here to investigate these mechanisms by studying the properties of the ISM in a unique sample of 8 extreme star-forming galaxies (SFGs) that have the highest excitation in the SDSS spectral data base. These dwarf SFGs have considerably lower stellar masses and metallicities, and higher equivalent widths and [OIII]5007/[OII]3727 ratios compared to all nearby SFGs with Lyman alpha emission studied so far with COS. They are, however, very similar to the dwarf Lyman alpha emitters at redshifts 3-6, which are thought to be the main sources of reionization in the early Universe. By combining the HST/COS UV data with data in the optical range, and using photoionization and radiative transfer codes, we will be able to study the properties of the Lyman alpha in these unique objects, derive column densities of the neutral hydrogen N(HI) and compare them with N(HI) obtained from the HeI emission-line ratios in the optical spectra. We will derive Lyman alpha escape fractions and indirectly Lyman continuum escape fractions.

  3. Measurement of boron isotope ratios in groundwater studies

    International Nuclear Information System (INIS)

    Porteous, N.C.; Walsh, J.N.; Jarvis, K.E.

    1995-01-01

    Boron is present at low levels in groundwater and rainfall in the UK, ranging between 2 and 200 ng ml -1 . A sensitive technique has been developed using inductively coupled plasma mass spectrometry (ICP-MS) to measure boron isotope ratios at low concentrations with a precision (s r ) of between 0.1 and 0.2%. Samples were evaporated to increase elemental boron concentrations to 200 ng ml -1 and interfering matrix elements were removed by an adapted cation-exchange separation procedure. The validity of measuring boron isotopic ratios by ICP-MS at this concentration level is discussed in relation to the theoretical instrument precision attainable based on counting statistics. (author)

  4. Screening for anabolic steroids in urine of forensic cases using fully automated solid phase extraction and LC-MS-MS.

    Science.gov (United States)

    Andersen, David W; Linnet, Kristian

    2014-01-01

    A screening method for 18 frequently measured exogenous anabolic steroids and the testosterone/epitestosterone (T/E) ratio in forensic cases has been developed and validated. The method involves a fully automated sample preparation including enzyme treatment, addition of internal standards and solid phase extraction followed by analysis by liquid chromatography-tandem mass spectrometry (LC-MS-MS) using electrospray ionization with adduct formation for two compounds. Urine samples from 580 forensic cases were analyzed to determine the T/E ratio and occurrence of exogenous anabolic steroids. Extraction recoveries ranged from 77 to 95%, matrix effects from 48 to 78%, overall process efficiencies from 40 to 54% and the lower limit of identification ranged from 2 to 40 ng/mL. In the 580 urine samples analyzed from routine forensic cases, 17 (2.9%) were found positive for one or more anabolic steroids. Only seven different steroids including testosterone were found in the material, suggesting that only a small number of common steroids are likely to occur in a forensic context. The steroids were often in high concentrations (>100 ng/mL), and a combination of steroids and/or other drugs of abuse were seen in the majority of cases. The method presented serves as a fast and automated screening procedure, proving the suitability of LC-MS-MS for analyzing anabolic steroids. © The Author 2014. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  5. PTR-MS monitoring of volatiles fingerprint evolution during grape must cooking

    NARCIS (Netherlands)

    Dimitri, G.; Ruth, van S.M.; Sacchetti, G.; Piva, G.; Alewijn, M.; Arfelli, G.

    2013-01-01

    The main aim of this study was to investigate the effect of processing temperature on the evolution of volatiles during grape must concentration upon cooking. The evolution of the volatiles fingerprint of grape must heated at 80, 90, and 100 °C was studied by Proton Transfer Reaction Mass

  6. High acetone concentrations throughout the 0-12 km altitude range over the tropical rainforest in Surinam

    NARCIS (Netherlands)

    Poschl, U; Williams, J; Hoor, P; Fischer, H; Crutzen, PJ; Warneke, C; Holzinger, R; Hansel, A; Jordan, A; Lindinger, W; Scheeren, HA; Peters, W; Lelieveld, J

    Airborne measurements of acetone were performed over the tropical rainforest in Surinam (2 degrees -7 degrees N, 54 degrees -58 degrees W, 0-12 km altitude) during the LBA-CLAIRE campaign in March 1998, using a novel proton transfer reaction mass spectrometer (PTR-MS) that enables the on-line

  7. Field determination of biomass burning emission ratios and factors via open-path FTIR spectroscopy and fire radiative power assessment: headfire, backfire and residual smouldering combustion in African savannahs

    Directory of Open Access Journals (Sweden)

    M. J. Wooster

    2011-11-01

    Full Text Available Biomass burning emissions factors are vital to quantifying trace gas release from vegetation fires. Here we evaluate emissions factors for a series of savannah fires in Kruger National Park (KNP, South Africa using ground-based open path Fourier transform infrared (FTIR spectroscopy and an IR source separated by 150–250 m distance. Molecular abundances along the extended open path are retrieved using a spectral forward model coupled to a non-linear least squares fitting approach. We demonstrate derivation of trace gas column amounts for horizontal paths transecting the width of the advected plume, and find for example that CO mixing ratio changes of ~0.01 μmol mol−1 [10 ppbv] can be detected across the relatively long optical paths used here. Though FTIR spectroscopy can detect dozens of different chemical species present in vegetation fire smoke, we focus our analysis on five key combustion products released preferentially during the pyrolysis (CH2O, flaming (CO2 and smoldering (CO, CH4, NH3 processes. We demonstrate that well constrained emissions ratios for these gases to both CO2 and CO can be derived for the backfire, headfire and residual smouldering combustion (RSC stages of these savannah fires, from which stage-specific emission factors can then be calculated. Headfires and backfires often show similar emission ratios and emission factors, but those of the RSC stage can differ substantially. The timing of each fire stage was identified via airborne optical and thermal IR imagery and ground-observer reports, with the airborne IR imagery also used to derive estimates of fire radiative energy (FRE, allowing the relative amount of fuel burned in each stage to be calculated and "fire averaged" emission ratios and emission factors to be determined. These "fire averaged" metrics are dominated by the headfire contribution, since the FRE data indicate that the vast majority

  8. Analysis of phytochemical variations in dioecious Tinospora cordifolia stems using HPLC/QTOF MS/MS and UPLC/QqQLIT -MS/MS.

    Science.gov (United States)

    Bajpai, Vikas; Singh, Awantika; Chandra, Preeti; Negi, M P S; Kumar, Nikhil; Kumar, Brijesh

    2016-01-01

    The stem of dioecious Tinospora cordifolia (Menispermaceae) is a commonly used traditional Ayurvedic medicine in India having several therapeutic properties. To develop and validate LC-MS methods for the identification and simultaneous quantitation of various secondary metabolites and to study metabolomic variations in the stem of male and female plants. Ethanolic extract of stems were analysed by HPLC/ESI-QTOF-MS/MS for rapid screening of bioactive phytochemicals. High resolution MS and MS/MS in positive ESI mode were used for structural investigation of secondary metabolites. An UPLC/ESI-QqQ(LIT) -MS/MS method in MRM mode was developed and validated for the simultaneous quantitation of five bioactive alkaloids. Identification and characterisation of 36 metabolites including alkaloids, sesquiterpenes and phytoecdysteroids were performed using LC-MS and MS/MS techniques. The bioactive alkaloids such as jatrorrhizine, magnoflorine, isocorydine, palmatine and tetrahydropalmatine were successfully quantified in male and female plants. The mean abundances of magnoflorine jatrorrhizine, and oblongine were significantly (P Phytochemicals in the stem of male and female Tinospora cordifolia showed significant qualitative and quantitative variations. LC-MS and MS/MS methods can be used to differentiate between male and female plants based on their chemical profiles and quantities of the marker bioactive alkaloids. This chemical composition difference was also evident during vegetative stage when there were no male and female flowers. Copyright © 2015 John Wiley & Sons, Ltd.

  9. Determination of Glyphosate Levels in Breast Milk Samples from Germany by LC-MS/MS and GC-MS/MS

    NARCIS (Netherlands)

    Steinborn, Angelika; Alder, Lutz; Michalski, Britta; Zomer, Paul; Bendig, Paul; Martinez, Sandra Aleson; Mol, Hans G.J.; Class, Thomas J.; Costa Pinheiro, Nathalie

    2016-01-01

    This study describes the validation and application of two independent analytical methods for the determination of glyphosate in breast milk. They are based on liquid chromatography-tandem mass spectrometry (LC-MS/MS) and gas chromatography-tandem mass spectrometry (GC-MS/MS), respectively. For

  10. Neutron to proton ratios of quasiprojectile and midrapidity emission in the 58Ni+58Ni reaction at 52 MeV/nucleon

    International Nuclear Information System (INIS)

    Theriault, D.; Vallee, A.; Gingras, L.; Larochelle, Y.; Roy, R.; April, A.; Beaulieu, L.; Grenier, F.; Lemieux, F.; Moisan, J.; St-Pierre, C.; Turbide, S.; Samri, M.; Borderie, B.; Rivet, M. F.; Bougault, R.; Colin, J.; Cussol, D.; Durand, D.; Lecolley, J.F.

    2005-01-01

    By combining data from a charged particle 58 Ni+ 58 Ni experiment at 52 MeV/nucleon with an 36 Ar+ 58 Ni experiment at 50 MeV/nucleon for which free neutrons have been detected, an increase in the neutron to proton ratio of the whole nuclear material at midrapidity has been experimentally observed in the reaction 58 Ni+ 58 Ni at 52 MeV/nucleon. The neutron-to-proton ratio of the quasi-projectile emission is analyzed for the same reactions and is seen to decrease below the ratio of the initial system. Those observations suggest that an asymmetric exchange of neutrons and protons between the quasiprojectile and the midrapidity region exists

  11. Finding of pesticides in fashionable fruit juices by LC-MS/MS and GC-MS/MS.

    Science.gov (United States)

    Tran, Kevin; Eide, David; Nickols, Susan M; Cromer, Michele R; Sabaa-Srur, Armando; Smith, Robert E

    2012-10-15

    Products labelled as containing extracts from two mushrooms (cordyceps plus reishi) and the juices from açaí, goji, mangosteen, noni, pomegranate, and sea buckthorn have been analysed for 174 different pesticides, using the validated QuEChERS method for sample preparation and electrospray LC-MS/MS in the positive ion mode for analysis. Pesticides were found in 10 of the 21 samples analysed. Most pesticides found were below the tolerance levels (1-6 μg/g, depending on the pesticide), but some were not. This included boscalid, dimethomorph, iprovalicarb, pyridaben, pyrimethanil, and imazalil, for which there is no tolerance reported or zero tolerance in any fruit. However, genuine açaí that was harvested in the state of Pará and lyophilised in Rio de Janeiro had no detectable pesticides, when analysed by both LC-MS/MS and GC-MS/MS, which can detect 213 more pesticides and industrial chemicals. Likewise no pesticides were found in one sample each of cordyceps plus reishi, sea buckthorn and noni. Published by Elsevier Ltd.

  12. Laser ablation ICP-MS for quantitative biomedical applications

    International Nuclear Information System (INIS)

    Konz, Ioana; Fernandez, Beatriz; Fernandez, M.L.; Pereiro, Rosario; Sanz-Medel, Alfredo

    2012-01-01

    LA-ICP-MS allows precise, relatively fast, and spatially resolved measurements of elements and isotope ratios at trace and ultratrace concentration levels with minimal sample preparation. Over the past few years this technique has undergone rapid development, and it has been increasingly applied in many different fields, including biological and medical research. The analysis of essential, toxic, and therapeutic metals, metalloids, and nonmetals in biomedical tissues is a key task in the life sciences today, and LA-ICP-MS has proven to be an excellent complement to the organic MS techniques that are much more commonly employed in the biomedical field. In order to provide an appraisal of the fast progress that is occurring in this field, this review critically describes new developments for LA-ICP-MS as well as the most important applications of LA-ICP-MS, with particular emphasis placed on the quantitative imaging of elements in biological tissues, the analysis of heteroatom-tagged proteins after their separation and purification by gel electrophoresis, and the analysis of proteins that do not naturally have ICP-MS-detectable elements in their structures, thus necessitating the use of labelling strategies. (orig.)

  13. Environmental radioactivity research on the Fukushima Dai-ichi Nuclear Power Plant accident by ICP-MS

    International Nuclear Information System (INIS)

    Ohno, Takeshi; Muramatsu, Yasuyuki

    2015-01-01

    Inductively coupled plasma (ICP) is characterized by high ionization efficiency for almost all elements. Recently, a triple quadrupole ICP-MS (ICP-MS/MS) has been applied to the measurements of isotope ratios for ultra-low level radioisotopes. The ICP-MS/MS features an additional quadrupole mass filter situated in front of the octopole reaction cell and quadrupole mass filter, which allows only the analyte ion to enter the cell by rejecting all the other ions. In this manuscript, we review recent studies on environmental radioactivity in Fukushima achieved by ICP-MS/MS techniques. (author)

  14. Pediatric MS

    Science.gov (United States)

    ... Pediatric MS Share this page Facebook Twitter Email Pediatric MS Pediatric MS Pediatric MS Support Pediatric Providers ... system through the Pediatric MS Support Group . Treating pediatric MS In 2018 the U.S. Food and Drug ...

  15. Analysis of expiration gas in intensive care patients with SIRS/sepsis using proton-transfer-reaction-mass-spectrometry

    International Nuclear Information System (INIS)

    Bodrogi, F.B.M.

    2003-11-01

    In 1971, Pauling and co-workers were the first to detect volatile organic compounds (VOC) in human breath. Since then, a number of technical applications for breath gas analyses have been designed and processed, among them gas chromatography and proton transfer reaction-mass spectrometry (PTR-MS). Due to this technical progress it is meanwhile possible to correlate different kinds and stages of diseases with measurable changes in the patient's VOC profile. The aim of the present study was to investigate the composition of VOC in exhaled air of patients with sepsis via PTR-MS. To isolate distinct volatile organic compounds that may serve as clinical markers for the onset, the progress, as well as the outcome of the disease, the results obtained from septic patients were compared with two different control groups: 25 healthy, non-smoking volunteers enrolled in the day-case-surgery and 25 post-operative in-patients residing in post-anaesthetic care units (PACU). PTR-MS is capable to analyze VOC according to their molecular weight with a range between 21-230 Da. A total of 210 different masses has been detected in the present study. 54 masses were significantly different in exhaled air of septic patients as compared to healthy controls as well as post-operative patients. Among them, mass 69 representing isoprene might be of special interest for the diagnosis of sepsis. Although no exact biochemical properties of isoprene have been described to date, it is known that isoprene synthesis is increased in plants following exposure to oxidative stress. Chronic, systemic infectious diseases like sepsis are accompanied by the production of reactive oxygen species, indicating that isoprene might be increased in the course of sepsis, too. In the present study, isoprene values were markedly higher in septic patients as compared to PACU residents (3.3-fold increase in mean value) and to healthy volunteers (2.2-fold increase in mean value). In addition (and in contrast to other VOC

  16. UPLC-MS/MS based diagnostics for epithelial ovarian cancer using fully sialylated C4-binding protein.

    Science.gov (United States)

    Tanabe, Kazuhiro; Matsuo, Koji; Miyazawa, Masaki; Hayashi, Masaru; Ikeda, Masae; Shida, Masako; Hirasawa, Takeshi; Sho, Ryuichiro; Mikami, Mikio

    2018-05-01

    Serum levels of fully sialylated C4-binding protein (FS-C4BP) are remarkably elevated in patients with epithelial ovarian cancer (EOC) and can be used as a marker to distinguish ovarian clear cell carcinoma from endometrioma. This study aimed to develop a stable, robust and reliable liquid chromatography-hybrid mass spectrometry (UPLC-MS/MS) based diagnostic method that would generalize FS-C4BP as a clinical EOC biomarker. Glycopeptides derived from 20 μL of trypsin-digested serum glycoprotein were analyzed via UPLC equipped with an electrospray ionization time-of-flight mass spectrometer. This UPLC-MS/MS-based diagnostic method was optimized for FS-C4BP and validated using sera from 119 patients with EOC and 127 women without cancer. A1958 (C4BP peptide with two fully sialylated biantennary glycans) was selected as a marker of FS-C4BP because its level in serum was highest among FS-C4BP family members. Preparation and UPLC-MS/MS were optimized for A1958, and performance and robustness were significantly improved relative to our previous method. An area under the curve analysis of the FS-C4BP index receiver operating characteristic curve revealed that the ratio between A1958 and A1813 (C4BP peptide with two partially sialylated biantennary glycans) reached 85%. A combination of the FS-C4BP index and carbohydrate antigen-125 levels further enhanced the sensitivity and specificity. © 2017 The Authors. Biomedical Chromatography published by John Wiley & Sons Ltd.

  17. On the electron-ion temperature ratio established by collisionless shocks

    Science.gov (United States)

    Vink, Jacco; Broersen, Sjors; Bykov, Andrei; Gabici, Stefano

    2015-07-01

    Astrophysical shocks are often collisionless shocks, in which the changes in plasma flow and temperatures across the shock are established not through Coulomb interactions, but through electric and magnetic fields. An open question about collisionless shocks is whether electrons and ions each establish their own post-shock temperature (non-equilibration of temperatures), or whether they quickly equilibrate in the shock region. Here we provide a simple, thermodynamic, relation for the minimum electron-ion temperature ratios that should be expected as a function of Mach number. The basic assumption is that the enthalpy-flux of the electrons is conserved separately, but that all particle species should undergo the same density jump across the shock, in order for the plasma to remain charge neutral. The only form of additional electron heating that we allow for is adiabatic heating, caused by the compression of the electron gas. These assumptions result in an analytic treatment of expected electron-ion temperature ratio that agrees with observations of collisionless shocks: at low sonic Mach numbers, Ms ≲ 2, the electron-ion temperature ratio is close to unity, whereas for Mach numbers above Ms ≈ 60 the electron-ion temperature ratio asymptotically approaches a temperature ratio of Te/Ti = me/ ⟨ mi ⟩. In the intermediate Mach number range the electron-ion temperature ratio scales as Te/Ti ∝ Ms-2. In addition, we calculate the electron-ion temperature ratios under the assumption of adiabatic heating of the electrons only, which results in a higher electron-ion temperature ratio, but preserves the Te/Ti ∝ Ms-2 scaling. We also show that for magnetised shocks the electron-ion temperature ratio approaches the asymptotic value Te/Ti = me/ ⟨ mi ⟩ for lower magnetosonic Mach numbers (Mms), mainly because for a strongly magnetised shock the sonic Mach number is larger than the magnetosonic Mach number (Mms ≤ Ms). The predicted scaling of the electron

  18. Constraining a hybrid volatility basis-set model for aging of wood-burning emissions using smog chamber experiments: a box-model study based on the VBS scheme of the CAMx model (v5.40

    Directory of Open Access Journals (Sweden)

    G. Ciarelli

    2017-06-01

    Full Text Available In this study, novel wood combustion aging experiments performed at different temperatures (263 and 288 K in a ∼ 7 m3 smog chamber were modelled using a hybrid volatility basis set (VBS box model, representing the emission partitioning and their oxidation against OH. We combine aerosol–chemistry box-model simulations with unprecedented measurements of non-traditional volatile organic compounds (NTVOCs from a high-resolution proton transfer reaction mass spectrometer (PTR-MS and with organic aerosol measurements from an aerosol mass spectrometer (AMS. Due to this, we are able to observationally constrain the amounts of different NTVOC aerosol precursors (in the model relative to low volatility and semi-volatile primary organic material (OMsv, which is partitioned based on current published volatility distribution data. By comparing the NTVOC ∕ OMsv ratios at different temperatures, we determine the enthalpies of vaporization of primary biomass-burning organic aerosols. Further, the developed model allows for evaluating the evolution of oxidation products of the semi-volatile and volatile precursors with aging. More than 30 000 box-model simulations were performed to retrieve the combination of parameters that best fit the observed organic aerosol mass and O : C ratios. The parameters investigated include the NTVOC reaction rates and yields as well as enthalpies of vaporization and the O : C of secondary organic aerosol surrogates. Our results suggest an average ratio of NTVOCs to the sum of non-volatile and semi-volatile organic compounds of ∼ 4.75. The mass yields of these compounds determined for a wide range of atmospherically relevant temperatures and organic aerosol (OA concentrations were predicted to vary between 8 and 30 % after 5 h of continuous aging. Based on the reaction scheme used, reaction rates of the NTVOC mixture range from 3.0 × 10−11 to 4. 0 × 10−11 cm3 molec−1 s−1

  19. Digitized morphometric analysis of dental pulp of permanent mandibular second molar for age estimation of Davangere population.

    Science.gov (United States)

    Kumar, Nerella Narendra; Panchaksharappa, Mamatha Gowda; Annigeri, Rajeshwari G

    2016-04-01

    The aim of the present study is to estimate the age of Davangere population by evaluating the pulp to tooth area ratio (PTR) by using digitized intraoral periapical radiographs of permanent mandibular second molar. 400 intraoral periapical radiograph (IOPA) of permanent mandibular 2nd molar of both the sexes aged 14-60 years were used. Digital camera was used to image the radiographs. Images were computed and PTR was calculated by AUTOCAD software. Intra and Inter observer variability was also assessed. Regression analysis was used to estimate the age of an individual by taking PTR as dependent variable. The mean PTR of males and females was 0.10 ± 0.02 and 0.09 ± 0.02 respectively. Negative correlation was observed, when age was compared with PTR {r = -0.441, -0.406 & -0.419 among males, females and total subjects (p AUTOCAD software. Also high differences were observed between estimated and chronological age of 12 years which is not in the acceptable range. But it provides a new window for research in the forensic sciences in estimating the adult age. Copyright © 2016 Elsevier Ltd and Faculty of Forensic and Legal Medicine. All rights reserved.

  20. Modeling signal-to-noise ratio of otoacoustic emissions in workers exposed to different industrial noise levels

    Directory of Open Access Journals (Sweden)

    Parvin Nassiri

    2016-01-01

    Full Text Available Introduction: Noise is considered as the most common cause of harmful physical effects in the workplace. A sound that is generated from within the inner ear is known as an otoacoustic emission (OAE. Distortion-product otoacoustic emissions (DPOAEs assess evoked emission and hearing capacity. The aim of this study was to assess the signal-to-noise ratio in different frequencies and at different times of the shift work in workers exposed to various levels of noise. It was also aimed to provide a statistical model for signal-to-noise ratio (SNR of OAEs in different frequencies based on the two variables of sound pressure level (SPL and exposure time. Materials and Methods: This case–control study was conducted on 45 workers during autumn 2014. The workers were divided into three groups based on the level of noise exposure. The SNR was measured in frequencies of 1000, 2000, 3000, 4000, and 6000 Hz in both ears, and in three different time intervals during the shift work. According to the inclusion criterion, SNR of 6 dB or greater was included in the study. The analysis was performed using repeated measurements of analysis of variance, spearman correlation coefficient, and paired samples t-test. Results: The results showed that there was no statistically significant difference between the three exposed groups in terms of the mean values of SNR (P > 0.05. Only in signal pressure levels of 88 dBA with an interval time of 10:30–11:00 AM, there was a statistically significant difference between the right and left ears with the mean SNR values of 3000 frequency (P = 0.038. The SPL had a significant effect on the SNR in both the right and left ears (P = 0.023, P = 0.041. The effect of the duration of measurement on the SNR was statistically significant in both the right and left ears (P = 0.027, P < 0.001. Conclusion: The findings of this study demonstrated that after noise exposure during the shift, SNR of OAEs reduced from the

  1. Screening for Anabolic Steroids in Urine of Forensic Cases Using Fully Automated Solid Phase Extraction and LC–MS-MS

    DEFF Research Database (Denmark)

    Andersen, David Wederkinck; Linnet, Kristian

    2014-01-01

    and solid phase extraction followed by analysis by liquid chromatography-tandem mass spectrometry (LC-MS-MS) using electrospray ionization with adduct formation for two compounds. Urine samples from 580 forensic cases were analyzed to determine the T/E ratio and occurrence of exogenous anabolic steroids....... Extraction recoveries ranged from 77 to 95%, matrix effects from 48 to 78%, overall process efficiencies from 40 to 54% and the lower limit of identification ranged from 2 to 40 ng/mL. In the 580 urine samples analyzed from routine forensic cases, 17 (2.9%) were found positive for one or more anabolic...

  2. ALLocator: an interactive web platform for the analysis of metabolomic LC-ESI-MS datasets, enabling semi-automated, user-revised compound annotation and mass isotopomer ratio analysis.

    Science.gov (United States)

    Kessler, Nikolas; Walter, Frederik; Persicke, Marcus; Albaum, Stefan P; Kalinowski, Jörn; Goesmann, Alexander; Niehaus, Karsten; Nattkemper, Tim W

    2014-01-01

    Adduct formation, fragmentation events and matrix effects impose special challenges to the identification and quantitation of metabolites in LC-ESI-MS datasets. An important step in compound identification is the deconvolution of mass signals. During this processing step, peaks representing adducts, fragments, and isotopologues of the same analyte are allocated to a distinct group, in order to separate peaks from coeluting compounds. From these peak groups, neutral masses and pseudo spectra are derived and used for metabolite identification via mass decomposition and database matching. Quantitation of metabolites is hampered by matrix effects and nonlinear responses in LC-ESI-MS measurements. A common approach to correct for these effects is the addition of a U-13C-labeled internal standard and the calculation of mass isotopomer ratios for each metabolite. Here we present a new web-platform for the analysis of LC-ESI-MS experiments. ALLocator covers the workflow from raw data processing to metabolite identification and mass isotopomer ratio analysis. The integrated processing pipeline for spectra deconvolution "ALLocatorSD" generates pseudo spectra and automatically identifies peaks emerging from the U-13C-labeled internal standard. Information from the latter improves mass decomposition and annotation of neutral losses. ALLocator provides an interactive and dynamic interface to explore and enhance the results in depth. Pseudo spectra of identified metabolites can be stored in user- and method-specific reference lists that can be applied on succeeding datasets. The potential of the software is exemplified in an experiment, in which abundance fold-changes of metabolites of the l-arginine biosynthesis in C. glutamicum type strain ATCC 13032 and l-arginine producing strain ATCC 21831 are compared. Furthermore, the capability for detection and annotation of uncommon large neutral losses is shown by the identification of (γ-)glutamyl dipeptides in the same strains

  3. ALLocator: an interactive web platform for the analysis of metabolomic LC-ESI-MS datasets, enabling semi-automated, user-revised compound annotation and mass isotopomer ratio analysis.

    Directory of Open Access Journals (Sweden)

    Nikolas Kessler

    Full Text Available Adduct formation, fragmentation events and matrix effects impose special challenges to the identification and quantitation of metabolites in LC-ESI-MS datasets. An important step in compound identification is the deconvolution of mass signals. During this processing step, peaks representing adducts, fragments, and isotopologues of the same analyte are allocated to a distinct group, in order to separate peaks from coeluting compounds. From these peak groups, neutral masses and pseudo spectra are derived and used for metabolite identification via mass decomposition and database matching. Quantitation of metabolites is hampered by matrix effects and nonlinear responses in LC-ESI-MS measurements. A common approach to correct for these effects is the addition of a U-13C-labeled internal standard and the calculation of mass isotopomer ratios for each metabolite. Here we present a new web-platform for the analysis of LC-ESI-MS experiments. ALLocator covers the workflow from raw data processing to metabolite identification and mass isotopomer ratio analysis. The integrated processing pipeline for spectra deconvolution "ALLocatorSD" generates pseudo spectra and automatically identifies peaks emerging from the U-13C-labeled internal standard. Information from the latter improves mass decomposition and annotation of neutral losses. ALLocator provides an interactive and dynamic interface to explore and enhance the results in depth. Pseudo spectra of identified metabolites can be stored in user- and method-specific reference lists that can be applied on succeeding datasets. The potential of the software is exemplified in an experiment, in which abundance fold-changes of metabolites of the l-arginine biosynthesis in C. glutamicum type strain ATCC 13032 and l-arginine producing strain ATCC 21831 are compared. Furthermore, the capability for detection and annotation of uncommon large neutral losses is shown by the identification of (γ-glutamyl dipeptides in

  4. A sensitive LC-MS/MS method for measurement of organophosphorus pesticides and their oxygen analogs in air sampling matrices.

    Science.gov (United States)

    Armstrong, Jenna L; Dills, Russell L; Yu, Jianbo; Yost, Michael G; Fenske, Richard A

    2014-01-01

    A rapid liquid chromatography tandem mass spectrometry (LC-MS/MS) method has been developed for determination of levels of the organophosphorus (OP) pesticides chlorpyrifos (CPF), azinphos methyl (AZM), and their oxygen analogs chlorpyrifos-oxon (CPF-O) and azinphos methyl-oxon (AZM-O) on common active air sampling matrices. XAD-2 resin and polyurethane foam (PUF) matrices were extracted with acetonitrile containing stable-isotope labeled internal standards (ISTD). Analysis was accomplished in Multiple Reaction Monitoring (MRM) mode, and analytes in unknown samples were identified by retention time (±0.1 min) and qualifier ratio (±30% absolute) as compared to the mean of calibrants. For all compounds, calibration linearity correlation coefficients were ≥0.996. Limits of detection (LOD) ranged from 0.15-1.1 ng/sample for CPF, CPF-O, AZM, and AZM-O on active sampling matrices. Spiked fortification recoveries were 78-113% from XAD-2 active air sampling tubes and 71-108% from PUF active air sampling tubes. Storage stability tests also yielded recoveries ranging from 74-94% after time periods ranging from 2-10 months. The results demonstrate that LC-MS/MS is a sensitive method for determining these compounds from two different matrices at the low concentrations that can result from spray drift and long range transport in non-target areas following agricultural applications. In an inter-laboratory comparison, the limit of quantification (LOQ) for LC-MS/MS was 100 times lower than a typical gas chromatography-mass spectrometry (GC-MS) method.

  5. Impaired myocardial blood flow reserve in subjects with metabolic syndrome analyzed using positron emission tomography and N-13 labeled ammonia

    Energy Technology Data Exchange (ETDEWEB)

    Teragawa, Hiroki; Kihara, Yasuki [Hiroshima University Graduate School of Biomedical Sciences, Department of Cardiovascular Medicine, Hiroshima (Japan); Morita, Koichi; Tamaki, Nagara [Hokkaido University Graduate School of Medicine, Department of Nuclear Medicine, Sapporo (Japan); Shishido, Hiroki; Otsuka, Nobuaki; Hirokawa, Yutaka [Hiroshima Heiwa Clinic, Hiroshima (Japan); Chayama, Kazuaki [Hiroshima University Graduate School of Biomedical Sciences, Department of Molecular Science and Medicine, Hiroshima (Japan)

    2010-02-15

    Coronary vasomotor response might be impaired in metabolic syndrome (MS); however, the precise abnormality has not been elucidated. The aim of this study was to assess coronary-vasomotor response in MS subjects using N-13 labeled ammonia and positron emission tomography. Myocardial blood flow (MBF) was measured at rest and during adenosine infusion in MS subjects (n = 13, MS group) with no definite evidence of heart disease and in subjects without MS (n = 14, non-MS group). Coronary vascular resistance (CVR) was calculated by dividing the mean aortic blood pressure by MBF. Myocardial blood flow reserve (MFR) was calculated as the ratio of the MBF during adenosine infusion to that during rest. Blood chemical parameters were measured to evaluate their relationship with MFR. During adenosine infusion, MBF was lower (p = 0.0085) and CVR higher (p = 0.0128) in the MS group than in the non-MS group and MFR was significantly lower in the MS group than in the non-MS group (2.13 {+-} 0.99 vs. 3.38 {+-} 0.95, p = 0.0027). Multivariate analysis demonstrated that the homeostasis model assessment-insulin resistance (p < 0.05) and the presence of hypertension (p < 0.05) were independent determinants of MFR. The results indicate that MFR was impaired in MS subjects, suggesting that an abnormal coronary microvascular response occurred in these subjects. This abnormality may have been partially due to insulin resistance and hypertension. (orig.)

  6. Impaired myocardial blood flow reserve in subjects with metabolic syndrome analyzed using positron emission tomography and N-13 labeled ammonia

    International Nuclear Information System (INIS)

    Teragawa, Hiroki; Kihara, Yasuki; Morita, Koichi; Tamaki, Nagara; Shishido, Hiroki; Otsuka, Nobuaki; Hirokawa, Yutaka; Chayama, Kazuaki

    2010-01-01

    Coronary vasomotor response might be impaired in metabolic syndrome (MS); however, the precise abnormality has not been elucidated. The aim of this study was to assess coronary-vasomotor response in MS subjects using N-13 labeled ammonia and positron emission tomography. Myocardial blood flow (MBF) was measured at rest and during adenosine infusion in MS subjects (n = 13, MS group) with no definite evidence of heart disease and in subjects without MS (n = 14, non-MS group). Coronary vascular resistance (CVR) was calculated by dividing the mean aortic blood pressure by MBF. Myocardial blood flow reserve (MFR) was calculated as the ratio of the MBF during adenosine infusion to that during rest. Blood chemical parameters were measured to evaluate their relationship with MFR. During adenosine infusion, MBF was lower (p = 0.0085) and CVR higher (p = 0.0128) in the MS group than in the non-MS group and MFR was significantly lower in the MS group than in the non-MS group (2.13 ± 0.99 vs. 3.38 ± 0.95, p = 0.0027). Multivariate analysis demonstrated that the homeostasis model assessment-insulin resistance (p < 0.05) and the presence of hypertension (p < 0.05) were independent determinants of MFR. The results indicate that MFR was impaired in MS subjects, suggesting that an abnormal coronary microvascular response occurred in these subjects. This abnormality may have been partially due to insulin resistance and hypertension. (orig.)

  7. Increased Ratio of Electron Transport to Net Assimilation Rate Supports Elevated Isoprenoid Emission Rate in Eucalypts under Drought1[W][OPEN

    Science.gov (United States)

    Dani, Kaidala Ganesha Srikanta; Jamie, Ian McLeod; Prentice, Iain Colin; Atwell, Brian James

    2014-01-01

    Plants undergoing heat and low-CO2 stresses emit large amounts of volatile isoprenoids compared with those in stress-free conditions. One hypothesis posits that the balance between reducing power availability and its use in carbon assimilation determines constitutive isoprenoid emission rates in plants and potentially even their maximum emission capacity under brief periods of stress. To test this, we used abiotic stresses to manipulate the availability of reducing power. Specifically, we examined the effects of mild to severe drought on photosynthetic electron transport rate (ETR) and net carbon assimilation rate (NAR) and the relationship between estimated energy pools and constitutive volatile isoprenoid emission rates in two species of eucalypts: Eucalyptus occidentalis (drought tolerant) and Eucalyptus camaldulensis (drought sensitive). Isoprenoid emission rates were insensitive to mild drought, and the rates increased when the decline in NAR reached a certain species-specific threshold. ETR was sustained under drought and the ETR-NAR ratio increased, driving constitutive isoprenoid emission until severe drought caused carbon limitation of the methylerythritol phosphate pathway. The estimated residual reducing power unused for carbon assimilation, based on the energetic status model, significantly correlated with constitutive isoprenoid emission rates across gradients of drought (r2 > 0.8) and photorespiratory stress (r2 > 0.9). Carbon availability could critically limit emission rates under severe drought and photorespiratory stresses. Under most instances of moderate abiotic stress levels, increased isoprenoid emission rates compete with photorespiration for the residual reducing power not invested in carbon assimilation. A similar mechanism also explains the individual positive effects of low-CO2, heat, and drought stresses on isoprenoid emission. PMID:25139160

  8. Two-dimensional imaging of edge plasma electron density and temperature by the passive helium emission ratio technique in TJ-II

    International Nuclear Information System (INIS)

    De la Cal, E; Guasp, J

    2011-01-01

    An intensified visible camera looks tangentially at a poloidal limiter where helium recycles, acting as a wide neutral source, and the atomic line emission due to plasma excitation becomes strongly localized there. It includes a bifurcated coherent bundle, each end with a different interference filter to select helium atomic lines, so that two simultaneous filtered images are captured in one single frame. The object of the proposed technique is to apply the well-known helium-beam line-ratio technique to obtain from selected filtered images the two-dimensional (2D) edge plasma n e and T e . The code EIRENE was used to demonstrate that the helium emission from recycling neutrals dominates the emission for the lines of view passing close above the limiter. Since these chords are nearly parallel to magnetic field lines in the emission region, the images can be approximated to poloidal cuts of the plasma emission within the tolerances discussed in the paper. The absolute radial profiles of T e and n e obtained with the method presented here were checked in the TJ-II stellarator to be in relatively good agreement with other diagnostics within a wide range of plasma parameters for both ECRH and NBI plasmas. The method is finally used to get 2D images of edge plasma T e and n e .

  9. Detection of counterfeit antiviral drug Heptodin and classification of counterfeits using isotope amount ratio measurements by multicollector inductively coupled plasma mass spectrometry (MC-ICPMS) and isotope ratio mass spectrometry (IRMS).

    Science.gov (United States)

    Santamaria-Fernandez, Rebeca; Hearn, Ruth; Wolff, Jean-Claude

    2009-06-01

    Isotope ratio mass spectrometry (IRMS) and multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) are highly important techniques that can provide forensic evidence that otherwise would not be available. MC-ICP-MS has proved to be a very powerful tool for measuring high precision and accuracy isotope amount ratios. In this work, the potential of combining isotope amount ratio measurements performed by MC-ICP-MS and IRMS for the detection of counterfeit pharmaceutical tablets has been investigated. An extensive study for the antiviral drug Heptodin has been performed for several isotopic ratios combining MC-ICP-MS and an elemental analyser EA-IRMS for stable isotope amount ratio measurements. The study has been carried out for 139 batches of the antiviral drug and analyses have been performed for C, S, N and Mg isotope ratios. Authenticity ranges have been obtained for each isotopic system and combined to generate a unique multi-isotopic pattern only present in the genuine tablets. Counterfeit tablets have then been identified as those tablets with an isotopic fingerprint outside the genuine isotopic range. The combination of those two techniques has therefore great potential for pharmaceutical counterfeit detection. A much greater power of discrimination is obtained when at least three isotopic systems are combined. The data from these studies could be presented as evidence in court and therefore methods need to be validated to support their credibility. It is also crucial to be able to produce uncertainty values associated to the isotope amount ratio measurements so that significant differences can be identified and the genuineness of a sample can be assessed.

  10. Selective measurements of isoprene and 2-methyl-3-buten-2-ol based on NO+ ionization mass spectrometry

    Directory of Open Access Journals (Sweden)

    W. Jud

    2012-12-01

    Full Text Available Biogenic VOC emissions are often dominated by 2-methyl-1,3-butadiene (isoprene and 2-methyl-3-buten-2-ol (232 MBO. Here we explore the possibility to selectively distinguish these species using NO+ as a primary ion in a conventional PTR-MS equipped with an SRI unit. High purity of NO+ (>90% as a primary ion was utilized in laboratory and field experiments using a conventional PTR-TOF-MS. Isoprene is ionized via charge transfer leading to the major product ion C5H8+ (>99% (e.g. Spanel and Smith, 1998. 232 MBO undergoes a hydroxide ion transfer reaction resulting in the major product ion channel C5H9+ (>95% (e.g. Amelynck et al., 2005. We show that both compounds are ionized with little fragmentation (>5% under standard operating conditions. Typical sensitivities of 11.1 ± 0.1 (isoprene and 12.9 ± 0.1 (232 MBO ncps ppbv−1 were achieved, which correspond to limit of detections of 18 and 15 pptv respectively for a 10 s integration time. Sensitivities decreased at higher collisional energies. Calibration experiments showed little humidity dependence. We tested the setup at a field site in Colorado dominated by ponderosa pine, a 232 MBO emitting plant species. Our measurements confirm 232 MBO as the dominant biogenic VOC at this site, exhibiting typical average daytime concentrations between 0.2–1.4 ppbv. The method is able to detect the presence of trace levels of isoprene at this field site (90–250 ppt without any interference from 232 MBO, which would not be feasible using H3O+ ionization chemistry, and which currently also remains a challenge for other analytical techniques (e.g. gas chromatographic methods.

  11. Tracing the link between plant volatile organic compound emissions and CO2 fluxes and by stable isotopes

    Science.gov (United States)

    Werner, Christiane; Wegener, Frederik; Jardine, Kolby

    2015-04-01

    The vegetation exerts a large influence on the atmosphere through the emission of volatile organic compounds (VOCs) and the emission and uptake of the greenhouse gas CO2. Despite the enormous importance, processes controlling plant carbon allocation into primary and secondary metabolism, such as photosynthetic carbon uptake, respiratory CO2 emission and VOC synthesis, remains unclear. Moreover, vegetation-atmosphere CO2 exchange is associated with a large isotopic imprint due to photosynthetic carbon isotope discrimination and 13C-fractionation during respiratory CO2 release1. The latter has been proposed to be related to carbon partitioning in the metabolic branching points of the respiratory pathways and secondary metabolism, which are linked via a number of interfaces including the central metabolite pyruvate. Notably, it is a known substrate in a large array of secondary pathways leading to the biosynthesis of many volatile organic compounds (VOCs), such as volatile isoprenoids, oxygenated VOCs, aromatics, fatty acid oxidation products, which can be emitted by plants. Here we investigate the linkage between VOC emissions, CO2 fluxes and associated isotope effects based on simultaneous real-time measurements of stable carbon isotope composition of branch respired CO2 (CRDS) and VOC fluxes (PTR-MS). We utilized positionally specific 13C-labeled pyruvate branch feeding experiments in the mediterranean shrub (Halimium halimifolium) to trace the partitioning of C1, C2, and C3 carbon atoms of pyruvate into VOCs versus CO2 emissions in the light and in the dark. In the light, we found high emission rates of a large array of VOC including volatile isoprenoids, oxygenated VOCs, green leaf volatiles, aromatics, sulfides, and nitrogen containing VOCs. These observations suggest that in the light, H. halimifolium dedicates a high carbon flux through secondary biosynthetic pathways including the pyruvate dehydrogenase bypass, mevalonic acid, MEP/DOXP, shikimic acid, and

  12. GoAmazon 2014/15. SRI-PTR-ToFMS Field Campaign Report

    Energy Technology Data Exchange (ETDEWEB)

    Guenther, A. [Univ. of California, Irvine, CA (United States)

    2016-03-01

    Our science team, including Dr. Alex Guenther (previously at Pacific Northwest National Laboratory (PNNL) and now at the University of California, Irvine) Dr. Saewung Kim and Dr. Roger Seco, and Dr. Jim Smith (previously at NCAR and now at UC Irvine), deployed a selected reagent ion – proton transfer reaction – time-of-flight mass spectrometer (SRI-PTR-TOFMS) to the T3 site during the GoAmazon study. One of the major uncertainties in climate model simulations is the effects of aerosols on radiative forcing, and a better understanding of the factors controlling aerosol distributions and life cycle is urgently needed. Aerosols contribute directly to the Earth’s radiation balance by scattering or absorbing light as a function of their physical properties and indirectly through particle-cloud interactions that lead to cloud formation and the modification of cloud properties. On a global scale, the dominant source of organic aerosol is biogenic volatile organic compounds (BVOC) emitted from terrestrial ecosystems. These organic aerosols are a major part of the total mass of all airborne particles and are currently not sufficiently represented in climate models. To incorporate quantitatively the effects of BVOCs and their oxidation products on biogenic organic aerosol (BOA) requires parameterization of their production in terrestrial ecosystems and their atmospheric transformations. This project was designed to reduce the gaps in our understanding of how these processes control BVOCs and BOAs, and their impact on climate. This was accomplished by wet and dry season measurements at the U.S. Department of Energy (DOE)’s Atmospheric Radiation Measurement (ARM) Climate Research Facility T3 site along with a comprehensive suite of complementary measurements. The specific goals were to 1) measure and mechanistically understand the factors affecting aerosol distributions over a tropical rain forest, especially the effects of anthropogenic pollution as a perturbation to

  13. End-group characterisation of poly(propylene glycol)s by means of electrospray ionisation-tandem mass spectrometry (ESI-MS/MS).

    Science.gov (United States)

    Jackson, Anthony T; Slade, Susan E; Thalassinos, Konstantinos; Scrivens, James H

    2008-10-01

    The end-group functionalisation of a series of poly(propylene glycol)s has been characterised by means of electrospray ionisation-tandem mass spectrometry (ESI-MS/MS). A series of peaks with mass-to-charge ratios that are close to that of the precursor ion were used to generate information on the end-group functionalities of the poly(propylene glycol)s. Fragment ions resulting from losses of both of the end groups were noted from some of the samples. An example is presented of how software can be used to significantly reduce the length of time involved in data interpretation (which is typically the most time-consuming part of the analysis).

  14. Summit CO2 emission rates by the CO2/SO2 ratio method at Kīlauea Volcano, Hawaiʻi, during a period of sustained inflation

    Science.gov (United States)

    Hager, S.A.; Gerlach, T.M.; Wallace, P.J.

    2008-01-01

    The emission rate of carbon dioxide escaping from the summit of Kīlauea Volcano, Hawaiʻi, proved highly variable, averaging 4900 ± 2000 metric tons per day (t/d) in June–July 2003 during a period of summit inflation. These results were obtained by combining over 90 measurements of COSPEC-derived SO2emission rates with synchronous CO2/SO2 ratios of the volcanic gas plume along the summit COSPEC traverse. The results are lower than the CO2 emission rate of 8500 ± 300 t/d measured by the same method in 1995–1999 during a period of long-term summit deflation [Gerlach, T.M., McGee, K.A., Elias, T., Sutton, A.J. and Doukas, M.P., 2002. Carbon dioxide emission rate of Kīlauea Volcano: Implications for primary magma and the summit reservoir. Journal of Geophysical Research-Solid Earth, 107(B9): art. no.-2189.]. Analysis of the data indicates that the emission rates of the present study likely reflect changes in the magma supply rate and residence time in the summit reservoir. It is also likely that emission rates during the inflation period were heavily influenced by SO2 pulses emitted adjacent to the COSPEC traverse, which biased CO2/SO2 ratios towards low values that may be unrepresentative of the global summit gas plume. We conclude that the SO2 pulses are consequences of summit re-inflation under way since 2003 and that CO2 emission rates remain comparable to, but more variable than, those measured prior to re-inflation.

  15. Rapid "breath-print" of liver cirrhosis by proton transfer reaction time-of-flight mass spectrometry. A pilot study.

    Directory of Open Access Journals (Sweden)

    Filomena Morisco

    Full Text Available UNLABELLED: The aim of the present work was to test the potential of Proton Transfer Reaction Time-of-Flight Mass Spectrometry (PTR-ToF-MS in the diagnosis of liver cirrhosis and the assessment of disease severity by direct analysis of exhaled breath. Twenty-six volunteers have been enrolled in this study: 12 patients (M/F 8/4, mean age 70.5 years, min-max 42-80 years with liver cirrhosis of different etiologies and at different severity of disease and 14 healthy subjects (M/F 5/9, mean age 52.3 years, min-max 35-77 years. Real time breath analysis was performed on fasting subjects using a buffered end-tidal on-line sampler directly coupled to a PTR-ToF-MS. Twelve volatile organic compounds (VOCs resulted significantly differently in cirrhotic patients (CP compared to healthy controls (CTRL: four ketones (2-butanone, 2- or 3- pentanone, C8-ketone, C9-ketone, two terpenes (monoterpene, monoterpene related, four sulphur or nitrogen compounds (sulfoxide-compound, S-compound, NS-compound, N-compound and two alcohols (heptadienol, methanol. Seven VOCs (2-butanone, C8-ketone, a monoterpene, 2,4-heptadienol and three compounds containing N, S or NS resulted significantly differently in compensate cirrhotic patients (Child-Pugh A; CP-A and decompensated cirrhotic subjects (Child-Pugh B+C; CP-B+C. ROC (Receiver Operating Characteristic analysis was performed considering three contrast groups: CP vs CTRL, CP-A vs CTRL and CP-A vs CP-B+C. In these comparisons monoterpene and N-compound showed the best diagnostic performance. CONCLUSIONS: Breath analysis by PTR-ToF-MS was able to distinguish cirrhotic patients from healthy subjects and to discriminate those with well compensated liver disease from those at more advanced severity stage. A breath-print of liver cirrhosis was assessed for the first time.

  16. Time resolved investigations on biogenic trace gases exchanges using proton-transfer-reaction mass spectrometry

    International Nuclear Information System (INIS)

    Karl, T.

    2000-02-01

    Volatile organic compounds (VOCs) released from vegetation, including wound-induced VOCs, can have important effects on atmospheric chemistry. The analytical methods for measuring wound-induced VOCs, especially the hexenal family of VOCs (hexenals, hexenols and hexenyl esters) but also compounds like acetaldehyde, are complicated by their chemical instability and the transient nature of their formation after leaf and stem wounding. The goal of this thesis was to assess, quantify and complement our understanding on the origin of tropospheric VOCs. This thesis demonstrates that formation and emission of hexenal family compounds can be monitored on-line using proton-transfer-reaction mass spectrometry (PTR-MS), avoiding the need for preconcentration or chromatography. These measurements revealed the rapid emission of the parent compound, (Z)-3-hexenal, within 1-2 seconds of wounding of leaves from various woody and nonwoody plants, and its metabolites including (E)-2-hexenal, hexenols and hexenyl acetates. Emission of (Z)-3-hexenal from detached, drying leaves averaged 500 μg (gram dry weight)-1. PTR-MS showed to be a useful tool for the analysis of VOC emissions resulting from grazing, herbivory, harvesting and senescing leaves. The release of reactive VOCs during lawn mowing was observed in on-line ambient air measurements in July and August 1998 in the outskirts of Innsbruck. Also obtained were data on emission rates of reactive aldehydes (hexenyl compounds) and other abundant VOCs such as methanol, acetaldehyde and acetone from drying grass in various chamber experiments. Fluxes were measured after cutting of grass using eddy covariance measurements and the micrometeorological gradient method (Obhukov-Similarity-Method). Comparison of data obtained by these different methods showed satisfactory agreement. The highest fluxes for methanol during drying were 5 mg/m2h, for (Z)-3-hexenal 1.5 mg/m2h. Experiments conducted on the Sonnblick Observatory in Fall and Winter

  17. LC-MS-MS Measurements of Urinary Creatinine and the Application of Creatinine Normalization Technique on Cotinine in Smokers’ 24 Hour Urine

    Directory of Open Access Journals (Sweden)

    Hongwei Hou

    2012-01-01

    Full Text Available A simple and sensitive high performance liquid chromatography-tandem mass spectrometry (HPLC-ESI-MS-MS method was developed and validated for the quantification of creatinine in human urine. The analysis was carried out on an Agilent Zorbax Eclipse XDB-C18 column (2.1×150 mm, 3.5 μm. The mobile phase was 0.1% formic acid in water and 0.1% formic acid in acetonitrile (50/50, v/v. Linear calibration curves were obtained in the concentration range of 1–2000.0 ng/mL, with a lower limit of quantification of 0.99 ng/mL. The intra- and interday precision (RSD values were below 3%. The method was successfully applied to a bioequivalence study of creatinine in Chinese smokers and nonsmokers. The total cotinine in 24 h urine and cotinine : creatinine ratio were also positively associated (Pearson R=0.942, P<0.0001. However, cotinine : creatinine ratio varied significantly across smoking groups for the difference of individual. 24 h urinary cotinine was more appropriate for expressing correlation with tar than cotinine : creatinine ratio.

  18. Dansyl-peptides matrix-assisted laser desorption/ionization mass spectrometric (MALDI-MS) and tandem mass spectrometric (MS/MS) features improve the liquid chromatography/MALDI-MS/MS analysis of the proteome.

    Science.gov (United States)

    Chiappetta, Giovanni; Ndiaye, Sega; Demey, Emmanuelle; Haddad, Iman; Marino, Gennaro; Amoresano, Angela; Vinh, Joëlle

    2010-10-30

    Peptide tagging is a useful tool to improve matrix-assisted laser desorption/ionization tandem mass spectrometric (MALDI-MS/MS) analysis. We present a new application of the use of the dansyl chloride (DNS-Cl). DNS-Cl is a specific primary amine reagent widely used in protein biochemistry. It adds a fluorescent dimethylaminonaphthalene moiety to the molecule. The evaluation of MALDI-MS and MS/MS analyses of dansylated peptides shows that dansylation raises the ionization efficiency of the most hydrophilic species compared with the most hydrophobic ones. Consequently, higher Mascot scores and protein sequence coverage are obtained by combining MS and MS/MS data of native and tagged samples. The N-terminal DNS-Cl sulfonation improves the peptide fragmentation and promotes the generation of b-fragments allowing better peptide sequencing. In addition, we set up a labeling protocol based on the microwave chemistry. Peptide dansylation proved to be a rapid and cheap method to improve the performance of liquid chromatography (LC)/MALDI-MS/MS analysis at the proteomic scale in terms of peptide detection and sequence coverage. Copyright © 2010 John Wiley & Sons, Ltd.

  19. Revealing the glycation sites in synthetic neoglycoconjugates formed by conjugation of the antigenic monosaccharide hapten of Vibrio cholerae O1, serotype Ogawa with the BSA protein carrier using LC-ESI-QqTOF-MS/MS

    Science.gov (United States)

    Jahouh, Farid; Saksena, Rina; Kováč, Pavol; Banoub, Joseph

    2012-01-01

    In this manuscript, we present the determination of glycation sites in synthetic neoglycoconjugates formed by conjugation of the antigenic monosaccharide hapten of Vibrio cholerae O1 serotype Ogawa to BSA using nano- liquid chromatography electrospray ionization quadrupole time-of-flight tandem mass spectroscopy (LC-ESI-QqTOF-MS/MS). The matrix-assisted laser desorption/ionization-TOF/TOF-MS/MS analyses of the tryptic digests of the glycoconjugates having a hapten:BSA ratio of 4.3:1, 6.6:1 and 13.2:1 revealed only three glycation sites, on the following lysine residues: Lys 235, Lys 437 and Lys 455. Digestion of the neoglycoconjugates with the proteases trypsin and GluC V8 gave complementary structural information and was shown to maximize the number of recognized glycation sites. Here, we report identification of 20, 27 and 33 glycation sites using LC-ESI-QqTOF-MS/MS analysis of a series of synthetic neoglycoconjugates with a hapten:BSA ratio of, respectively, 4.3:1, 6.6:1 and 13.2:1. We also tentatively propose that all the glycated lysine residues are located mainly near the outer surface of the protein. PMID:22791257

  20. BVOC ecosystem flux measurements at a high latitude wetland site

    Directory of Open Access Journals (Sweden)

    T. Holst

    2010-02-01

    Full Text Available In this study, we present summertime concentrations and fluxes of biogenic volatile organic compounds (BVOCs measured at a sub-arctic wetland in northern Sweden using a disjunct eddy-covariance (DEC technique based on a proton transfer reaction mass spectrometer (PTR-MS. The vegetation at the site was dominated by Sphagnum, Carex and extit{Eriophorum} spp. The measurements reported here cover a period of 50 days (1 August to 19 September 2006, approximately one half of the growing season at the site, and allowed to investigate the effect of day-to-day variation in weather as well as of vegetation senescence on daily BVOC fluxes, and on their temperature and light responses. The sensitivity drift of the DEC system was assessed by comparing H3O+-ion cluster formed with water molecules (H3O+(H2O at m37 with water vapour concentration measurements made using an adjacent humidity sensor, and the applicability of the DEC method was analysed by a comparison of sensible heat fluxes for high frequency and DEC data obtained from the sonic anemometer. These analyses showed no significant PTR-MS sensor drift over a period of several weeks and only a small flux-loss due to high-frequency spectrum omissions. This loss was within the range expected from other studies and the theoretical considerations.

    Standardised (20 °C and 1000 μmol m−2 s−1 PAR summer isoprene emission rates found in this study of 329 μg C m−2 (ground area h−1 were comparable with findings from more southern boreal forests, and fen-like ecosystems. On a diel scale, measured fluxes indicated a stronger temperature dependence than emissions from temperate or (subtropical ecosystems. For the first time, to our knowledge, we report ecosystem methanol fluxes from a sub-arctic ecosystem. Maximum daytime emission fluxes were around 270 μg m−2 h−1

  1. Inductively coupled plasma – Tandem mass spectrometry (ICP-MS/MS): A powerful and universal tool for the interference-free determination of (ultra)trace elements – A tutorial review

    Energy Technology Data Exchange (ETDEWEB)

    Balcaen, Lieve; Bolea-Fernandez, Eduardo [Ghent University, Department of Analytical Chemistry, Krijgslaan 281-S12, B-9000 Ghent (Belgium); Resano, Martín [University of Zaragoza, Department of Analytical Chemistry, Pedro Cerbuna 12, E-50009 Zaragoza (Spain); Vanhaecke, Frank, E-mail: Frank.Vanhaecke@UGent.be [Ghent University, Department of Analytical Chemistry, Krijgslaan 281-S12, B-9000 Ghent (Belgium)

    2015-09-24

    This paper is intended as a tutorial review on the use of inductively coupled plasma – tandem mass spectrometry (ICP-MS/MS) for the interference-free quantitative determination and isotope ratio analysis of metals and metalloids in different sample types. Attention is devoted both to the instrumentation and to some specific tools and procedures available for advanced method development. Next to the more typical reaction gases, e.g., H{sub 2}, O{sub 2} and NH{sub 3}, also the use of promising alternative gases, such as CH{sub 3}F, is covered, and the possible reaction pathways with those reactive gases are discussed. A variety of published applications relying on the use of ICP-MS/MS are described, to illustrate the added value of tandem mass spectrometry in (ultra)trace analysis. - Highlights: • First review on tandem ICP-mass spectrometry (ICP-MS/MS). • Clear description of operating principles of ICP-MS/MS. • Description on how to make use of product ion scans, precursor ion scans and neutral gain scans in method development. • Overview of applications published so far.

  2. Inductively coupled plasma – Tandem mass spectrometry (ICP-MS/MS): A powerful and universal tool for the interference-free determination of (ultra)trace elements – A tutorial review

    International Nuclear Information System (INIS)

    Balcaen, Lieve; Bolea-Fernandez, Eduardo; Resano, Martín; Vanhaecke, Frank

    2015-01-01

    This paper is intended as a tutorial review on the use of inductively coupled plasma – tandem mass spectrometry (ICP-MS/MS) for the interference-free quantitative determination and isotope ratio analysis of metals and metalloids in different sample types. Attention is devoted both to the instrumentation and to some specific tools and procedures available for advanced method development. Next to the more typical reaction gases, e.g., H_2, O_2 and NH_3, also the use of promising alternative gases, such as CH_3F, is covered, and the possible reaction pathways with those reactive gases are discussed. A variety of published applications relying on the use of ICP-MS/MS are described, to illustrate the added value of tandem mass spectrometry in (ultra)trace analysis. - Highlights: • First review on tandem ICP-mass spectrometry (ICP-MS/MS). • Clear description of operating principles of ICP-MS/MS. • Description on how to make use of product ion scans, precursor ion scans and neutral gain scans in method development. • Overview of applications published so far.

  3. Odorous gaseous emissions as influence by process condition for the forced aeration composting of pig slaughterhouse sludge

    Energy Technology Data Exchange (ETDEWEB)

    Blazy, V., E-mail: vincent.blazy@irstea.fr [Irstea, UR GERE, 17 Avenue de Cucillé, CS 64427, F-35044 Rennes (France); Guardia, A. de, E-mail: amaury.de-guardia@irstea.fr [Irstea, UR GERE, 17 Avenue de Cucillé, CS 64427, F-35044 Rennes (France); Benoist, J.C; Daumoin, M. [Irstea, UR GERE, 17 Avenue de Cucillé, CS 64427, F-35044 Rennes (France); Lemasle, M.; Wolbert, D. [Laboratoire Sciences Chimiques de Rennes - équipe Chimie et Ingénierie des Procédés, UMR 6226 CNRS, ENSCR, Avenue du Général Leclerc, 35700 Rennes (France); Barrington, S., E-mail: suzellebarrington@sympatico.ca [Irstea, UR GERE, 17 Avenue de Cucillé, CS 64427, F-35044 Rennes (France); Concordia University, Department of Building, Civil and Environmental Engineering, 1455 de Maisonneuve, Montréal, QC H3G 1M8 (Canada)

    2014-07-15

    Highlights: • The gaseous emissions produced by various composting process conditions were characterized and quantified. • Nine compounds were potentially odorous: TMA, NH{sub 3}, 2-pentanone, 1-propanol-2-methyl, acetophenone and sulphur forms. • The tested composting process conditions reduced odour emissions by a factor of 5–10. • A reduction of 10{sup 5} to 10{sup 6} is required to reach an odour threshold limit at peak event emissions. • Both aeration rate and bulking agent had the most impact on reducing odour emissions. - Abstract: Compost sustainability requires a better control of its gaseous emissions responsible for several impacts including odours. Indeed, composting odours have stopped the operation of many platforms and prevented the installation of others. Accordingly, present technologies collecting and treating gases emitted from composting are not satisfactory and alternative solutions must be found. Thus, the aim of this paper was to study the influence of composting process conditions on gaseous emissions. Pig slaughterhouse sludge mixed with wood chips was composted under forced aeration in 300 L laboratory reactors. The process conditions studied were: aeration rate of 1.68, 4.03, 6.22, 9.80 and 13.44 L/h/kg of wet sludge; incorporation ratio of 0.55, 0.83 and 1.1 (kg of wet wood chips/kg of wet sludge), and; bulking agent particles size of <10, 10 < 20 and 20 < 30 mm. Out-going gases were sampled every 2 days and their composition was analysed using gas chromatography coupled with mass spectrometry (GC–MS). Fifty-nine compounds were identified and quantified. Dividing the cumulated mass production over 30 days of composting, by odour threshold, 9 compounds were identified as main potential odour contributors: hydrogen sulphide, trimethylamine, ammonia, 2-pentanone, 1-propanol-2-methyl, dimethyl sulphide, dimethyl disulphide, dimethyl trisulphide and acetophenone. Five gaseous compounds were correlated with both aeration rate and

  4. Odorous gaseous emissions as influence by process condition for the forced aeration composting of pig slaughterhouse sludge

    International Nuclear Information System (INIS)

    Blazy, V.; Guardia, A. de; Benoist, J.C; Daumoin, M.; Lemasle, M.; Wolbert, D.; Barrington, S.

    2014-01-01

    Highlights: • The gaseous emissions produced by various composting process conditions were characterized and quantified. • Nine compounds were potentially odorous: TMA, NH 3 , 2-pentanone, 1-propanol-2-methyl, acetophenone and sulphur forms. • The tested composting process conditions reduced odour emissions by a factor of 5–10. • A reduction of 10 5 to 10 6 is required to reach an odour threshold limit at peak event emissions. • Both aeration rate and bulking agent had the most impact on reducing odour emissions. - Abstract: Compost sustainability requires a better control of its gaseous emissions responsible for several impacts including odours. Indeed, composting odours have stopped the operation of many platforms and prevented the installation of others. Accordingly, present technologies collecting and treating gases emitted from composting are not satisfactory and alternative solutions must be found. Thus, the aim of this paper was to study the influence of composting process conditions on gaseous emissions. Pig slaughterhouse sludge mixed with wood chips was composted under forced aeration in 300 L laboratory reactors. The process conditions studied were: aeration rate of 1.68, 4.03, 6.22, 9.80 and 13.44 L/h/kg of wet sludge; incorporation ratio of 0.55, 0.83 and 1.1 (kg of wet wood chips/kg of wet sludge), and; bulking agent particles size of <10, 10 < 20 and 20 < 30 mm. Out-going gases were sampled every 2 days and their composition was analysed using gas chromatography coupled with mass spectrometry (GC–MS). Fifty-nine compounds were identified and quantified. Dividing the cumulated mass production over 30 days of composting, by odour threshold, 9 compounds were identified as main potential odour contributors: hydrogen sulphide, trimethylamine, ammonia, 2-pentanone, 1-propanol-2-methyl, dimethyl sulphide, dimethyl disulphide, dimethyl trisulphide and acetophenone. Five gaseous compounds were correlated with both aeration rate and bulking agent

  5. MALDI-TOF MS/MS measurements of PMMA

    NARCIS (Netherlands)

    Becer, C.R.; Baumgaertel, A.; Gottschaldt, M.; Schubert, U.S.

    2008-01-01

    The polymer poly(Me methacrylate) (PMMA) was analyzed using the matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS) technique. The MALDI-TOF MS app. was coupled with a collision-induced dissocn. (CID) unit. The performance of the MALDI-TOF/TOF MS method in

  6. Analysis of oxcarbazepine and the 10-hydroxycarbazepine enantiomers in plasma by LC-MS/MS: application in a pharmacokinetic study.

    Science.gov (United States)

    de Jesus Antunes, Natalicia; Wichert-Ana, Lauro; Coelho, Eduardo Barbosa; Della Pasqua, Oscar; Alexandre, Veriano; Takayanagui, Osvaldo Massaiti; Tozatto, Eduardo; Lanchote, Vera Lucia

    2013-12-01

    Oxcarbazepine is a second-generation antiepileptic drug indicated as monotherapy or adjunctive therapy in the treatment of partial seizures or generalized tonic-clonic seizures in adults and children. It undergoes rapid presystemic reduction with formation of the active metabolite 10-hydroxycarbazepine (MHD), which has a chiral center at position 10, with the enantiomers (S)-(+)- and R-(-)-MHD showing similar antiepileptic effects. This study presents the development and validation of a method of sequential analysis of oxcarbazepine and MHD enantiomers in plasma using liquid chromatography with tandem mass spectrometry (LC-MS/MS). Aliquots of 100 μL of plasma were extracted with a mixture of methyl tert-butyl ether: dichloromethane (2:1). The separation of oxcarbazepine and the MHD enantiomers was obtained on a chiral phase Chiralcel OD-H column, using a mixture of hexane:ethanol:isopropanol (80:15:5, v/v/v) as mobile phase at a flow rate of 1.3 mL/min with a split ratio of 1:5, and quantification was performed by LC-MS/MS. The limit of quantification was 12.5 ng oxcarbazepine and 31.25 ng of each MHD enantiomer/mL of plasma. The method was applied in the study of kinetic disposition of oxcarbazepine and the MHD enantiomers in the steady state after oral administration of 300 mg/12 h oxcarbazepine in a healthy volunteer. The maximum plasma concentration of oxcarbazepine was 1.2 µg/mL at 0.75 h. The kinetic disposition of MHD is enantioselective, with a higher proportion of the S-(+)-MHD enantiomer compared to R-(-)-MHD and an AUC(0-12) S-(+)/R-(-) ratio of 5.44. © 2013 Wiley Periodicals, Inc.

  7. Direct coupling of a flow-flow electromembrane extraction probe to LC-MS

    DEFF Research Database (Denmark)

    Fuchs, David; Gabel-Jensen, Charlotte; Jensen, Henrik

    2016-01-01

    the fully automated EME-LC-MS system offers a significant time saving and in addition demonstrates increased sensitivity as the analytes were automatically enriched during the extraction process. The experiment revealed 6 to 16 times higher S/N ratios of the EME-LC-MS method compared to protein...... precipitation followed by LC-MS and thus concomitantly lower LOD and LOQ. The setup integrates a complete analytical workflow of rapid extraction, enrichment, separation and detection of analytes in a fully automated manner. These attributes make the developed system a powerful alternative approach for a wide...

  8. The need for a disease-specific prospective pregnancy registry for multiple sclerosis (MS).

    Science.gov (United States)

    Alwan, Sura; Chambers, Christina D; Armenti, Vincent T; Sadovnick, A Dessa

    2015-01-01

    Multiple sclerosis (MS) is the most commonly acquired neurological disorder affecting young adults of reproductive age with an approximately 3:1 female to male ratio. Although pregnancy is not contraindicated in MS, data are limited regarding pregnancy outcome among MS patients, and the safety or risk to the fetus associated with most maternal MS treatments, such as disease modifying therapies (DMTs), during pregnancy is unknown. We review available epidemiological and registry data on MS and pregnancy and discuss the need to initiate a North American Multiple Sclerosis Pregnancy Registry that will prospectively identify pregnancies in women with MS, obtain information on the disease, and its treatment during gestation and lactation and follow the children to determine their health status. Copyright © 2014 Elsevier B.V. All rights reserved.

  9. A DETAILED STUDY OF SPITZER-IRAC EMISSION IN HERBIG-HARO OBJECTS. I. MORPHOLOGY AND FLUX RATIOS OF SHOCKED EMISSION

    International Nuclear Information System (INIS)

    Takami, Michihiro; Karr, Jennifer L.; Chen, How-Huan; Lee, Hsu-Tai; Koh, Haegon

    2010-01-01

    We present a detailed analysis of Spitzer-IRAC images obtained toward six Herbig-Haro objects (HH 54/211/212, L 1157/1448, and BHR 71). Our analysis includes (1) comparisons of morphology between the four IRAC bands (3.6, 4.5, 5.8, and 8.0 μm) and H 2 1-0 S(1) at 2.12 μm for three out of six objects, (2) measurements of spectral energy distributions (SEDs) at selected positions, and (3) comparisons of these results with calculations of thermal H 2 emission at LTE (207 lines in four bands) and non-LTE (32-45 lines, depending on the particle for collisions). We show that the morphologies observed at 3.6 and 4.5 μm are similar to each other and to H 2 1-0 S(1). This is well explained by thermal H 2 emission at non-LTE if the dissociation rate is significantly larger than 0.002-0.02, allowing thermal collisions to be dominated by atomic hydrogen. In contrast, the 5.8 and 8.0 μm emission shows different morphologies from the others in some regions. This emission appears to be more enhanced at the wakes in bow shocks, or less enhanced in patchy structures in the jet. These tendencies are explained by the fact that thermal H 2 emission in the 5.8 and 8.0 μm band is enhanced in regions at lower densities and temperatures. Throughout, the observed similarities and differences in morphology between four bands and 1-0 S(1) are well explained by thermal H 2 emission. The observed SEDs are categorized into type-A, those in which the flux monotonically increases with wavelength, and type-B, those with excess emission at 4.5 μm. The type-A SEDs are explained by thermal H 2 emission, in particular with simple shock models with a power-law cooling function (Λ ∝ T s ). Our calculations suggest that the type-B SEDs require extra contaminating emission in the 4.5 μm band. The CO vibrational emission is the most promising candidate, and the other contaminants discussed to date (H I, [Fe II], fluorescent H 2 , and polycyclic aromatic hydrocarbon) are not likely to explain the

  10. Trace gas emissions from burning Florida wetlands

    Science.gov (United States)

    Cofer, Wesley R., III; Levine, Joel S.; Lebel, Peter J.; Winstead, Edward L.; Koller, Albert M., Jr.; Hinkle, C. Ross

    1990-01-01

    Measurements of biomass burn-produced trace gases were obtained using a helicopter at low altitudes above burning Florida wetlands on November 9, 1987, and from both helicopter and light-aircraft samplings on November 7, 1988. Carbon dioxide normalized emission ratios for carbon monoxide, hydrogen, methane, total nonmethane hydrocarbons, and nitrous oxide were obtained over burning graminoid wetlands consisting primarily of Spartina bakeri and Juncus roemerianus. Some interspersed scrub oak and saw palmetto were also burned. No significant differences were observed in the emission ratios determined for these gases from samples collected over flaming, mixed, and smoldering phases of combustion during the 1987 fire. Combustion-categorized differences in emission ratios were small for the 1988 fire. Combustion efficiency was relatively good (low emission ratios for reduced gases) for both fires. It is believed that the consistently low emission ratios were a unique result of graminoid wetlands fires, in which the grasses and rushes burned rapidly down to standing water and were quickly extinguished. Consequently, the efficiency of the combustion was good and the amount and duration of smoldering combustion was greatly deminished.

  11. Relative quantification of enantiomers of chiral amines by high-throughput LC–ESI-MS/MS using isotopic variants of light and heavy L-pyroglutamic acids as the derivatization reagents

    International Nuclear Information System (INIS)

    Mochizuki, Toshiki; Taniguchi, Sayuri; Tsutsui, Haruhito; Min, Jun Zhe; Inoue, Koichi; Todoroki, Kenichiro; Toyo’oka, Toshimasa

    2013-01-01

    Highlights: ► Development of chiral labeling reagent for a pair of amine enantiomers. ► High-throughput analysis of diastereomers by UPLC–ESI-MS/MS. ► Highly efficient separation and detection of the enantiomers. ► Differential analysis of enantiomer ratio in different sample groups using light and heavy labeling reagents. -- Abstract: L-Pyroglutamic acid (L-PGA) was evaluated as a chiral labeling reagent for the enantioseparation of chiral amines in terms of separation efficiency by reversed-phase chromatography and detection sensitivity by ESI-MS/MS. Several amines and amino acid methyl esters were used as typical representatives of the chiral amines. Both enantiomers of the chiral amines were easily labeled with L-PGAs at room temperature for 60 min in the presence of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and 1-hydroxy-1H-benzotriazole as the activation reagents. The resulting diastereomers were completely separated by reversed-phase chromatography using the small particle (1.7 μm) ODS column (Rs = 1.6–6.8). A highly sensitive detection at a low-fmol level (1–4 fmol) was also obtained from the multiple reaction monitoring (MRM) chromatograms. Therefore, a high-throughput determination was achieved by the present UPLC–ESI-MS/MS method. An isotope labeling strategy using light and heavy L-PGAs for the differential analysis of chiral amines in different sample groups was also proposed in this paper. As a model study, the differential analysis of the R and S ratio of 1-phenylethylamine (PEA) was performed according to the proposed procedure using light and heavy reagents, i.e., L-PGA and L-PGA-d 5 . The R/S ratio of PEA, spiked at the different concentrations in rat plasma, was almost similar to the theoretical values. Consequently, the proposed strategy using light and heavy chiral labeling reagents seems to be applicable for the differential analysis of chiral amine enantiomers in different sample groups, such as healthy persons and

  12. Biogenic volatile organic compound and respiratory CO2 emissions after 13C-labeling: online tracing of C translocation dynamics in poplar plants.

    Science.gov (United States)

    Ghirardo, Andrea; Gutknecht, Jessica; Zimmer, Ina; Brüggemann, Nicolas; Schnitzler, Jörg-Peter

    2011-02-28

    Globally plants are the primary sink of atmospheric CO(2), but are also the major contributor of a large spectrum of atmospheric reactive hydrocarbons such as terpenes (e.g. isoprene) and other biogenic volatile organic compounds (BVOC). The prediction of plant carbon (C) uptake and atmospheric oxidation capacity are crucial to define the trajectory and consequences of global environmental changes. To achieve this, the biosynthesis of BVOC and the dynamics of C allocation and translocation in both plants and ecosystems are important. We combined tunable diode laser absorption spectrometry (TDLAS) and proton transfer reaction mass spectrometry (PTR-MS) for studying isoprene biosynthesis and following C fluxes within grey poplar (Populus x canescens) saplings. This was achieved by feeding either (13)CO(2) to leaves or (13)C-glucose to shoots via xylem uptake. The translocation of (13)CO(2) from the source to other plant parts could be traced by (13)C-labeled isoprene and respiratory (13)CO(2) emission. In intact plants, assimilated (13)CO(2) was rapidly translocated via the phloem to the roots within 1 hour, with an average phloem transport velocity of 20.3±2.5 cm h(-1). (13)C label was stored in the roots and partially reallocated to the plants' apical part one day after labeling, particularly in the absence of photosynthesis. The daily C loss as BVOC ranged between 1.6% in mature leaves and 7.0% in young leaves. Non-isoprene BVOC accounted under light conditions for half of the BVOC C loss in young leaves and one-third in mature leaves. The C loss as isoprene originated mainly (76-78%) from recently fixed CO(2), to a minor extent from xylem-transported sugars (7-11%) and from photosynthetic intermediates with slower turnover rates (8-11%). We quantified the plants' C loss as respiratory CO(2) and BVOC emissions, allowing in tandem with metabolic analysis to deepen our understanding of ecosystem C flux.

  13. Solid state cathodoluminescence and the properties of its two emission peaks

    International Nuclear Information System (INIS)

    Xu Xurong

    2007-01-01

    We discovered solid state cathodoluminescence (SSCL). For its identification we excluded all artifacts, carried out its cross proof and studied its generality. Its spectrum is characterized by the appearance of short wavelength peak when the applied voltage is increased. Three voltage ranges are distinguished, in the lower voltage range we have the long wavelength emission, in the middle range we have both long and short wavelength emissions, and in the higher voltage range we have only the short wavelength emission. The mechanism of this spectral shift lies in the electrical field ionization of excitons. This effect initiates the applicability of band model besides molecular excitons theory. The temporal behaviors of both peaks in SSCL are studied with a method of estimating lifetime by means of frequency dependence on intensity. The lifetime of short wavelength emission is found to be 5 ms and that of long wavelength emission is less than 0.05 ms

  14. Comparison of Protein Phosphatase Inhibition Assay with LC-MS/MS for Diagnosis of Microcystin Toxicosis in Veterinary Cases

    Directory of Open Access Journals (Sweden)

    Caroline E. Moore

    2016-03-01

    Full Text Available Microcystins are acute hepatotoxins of increasing global concern in drinking and recreational waters and are a major health risk to humans and animals. Produced by cyanobacteria, microcystins inhibit serine/threonine protein phosphatase 1 (PP1. A cost-effective PP1 assay using p-nitrophenyl phosphate was developed to quickly assess water and rumen content samples. Significant inhibition was determined via a linear model, which compared increasing volumes of sample to the log-transformed ratio of the exposed rate over the control rate of PP1 activity. To test the usefulness of this model in diagnostic case investigations, samples from two veterinary cases were tested. In August 2013 fifteen cattle died around two ponds in Kentucky. While one pond and three tested rumen contents had significant PP1 inhibition and detectable levels of microcystin-LR, the other pond did not. In August 2013, a dog became fatally ill after swimming in Clear Lake, California. Lake water samples collected one and four weeks after the dog presented with clinical signs inhibited PP1 activity. Subsequent analysis using liquid chromatography-mass spectrometry (LC-MS/MS detected microcystin congeners -LR, -LA, -RR and -LF but not -YR. These diagnostic investigations illustrate the advantages of using functional assays in combination with LC-MS/MS.

  15. Assessing and evaluating urban VOC emissions in mid-latitude megacities from intensive observations in Paris and Los Angeles

    Science.gov (United States)

    Borbon, A.; Gilman, J. B.; Kuster, W. C.; McKeen, S. A.; Holloway, J. S.; Gros, V.; Gaimoz, C.; Beekmann, M.; De Gouw, J. A.

    2011-12-01

    Volatile Organic Compounds (VOC) affect urban air quality and regional climate change by contributing to ozone formation and the build-up of Secondary Organic Aerosols (SOA). Quantification of VOC emissions is a first critical step to predict VOC environmental impacts and to design effective abatement strategies. Indeed, the quality of ozone and SOA forecasts strongly depends on an accurate knowledge of the primary VOC emissions. However, commonly used bottom-up approaches are highly uncertain due to source multiplicity (combustion processes, storage and distribution of fossil fuels, solvent use, etc.) because of numerous controlling factors (driving conditions, fuel type, temperature, radiation, etc.), and their great variability in time and space. Field observations of VOC and other trace gases can provide valuable top-down constraints to evaluate VOC emission inventories at urban scales. In addition, the implementation of emission reduction measures raises the question of the increasing importance of VOC sources other than traffic. Here, we will evaluate VOC emissions of two mid-latitude megacities in the Northern Hemisphere: the Greater Paris area (Europe) and Los Angeles (USA). In 2009 and 2010, three intensive field campaigns took place in Paris and Los Angeles in the framework of the MEGAPOLI (EU FP7) and CalNex-2010 projects, respectively. Very detailed measurements of aerosol composition and properties, and their gaseous VOC precursors were carried out at ground-based sites (urban center and suburban) and on various mobile platforms. This contribution uses a comprehensive suite of VOC measurements collected by GC-MS/FID techniques at ground-based sites in both cities by a source-receptor methodology. First, emission ratios were estimated from the observations (uncertainty of ± 20%) and compared regarding regional characteristics and European vs. Californian control policies. Then, determined emission ratios were used to assess the accuracy of up

  16. Determination of the glycation sites of Bacillus anthracis neoglycoconjugate vaccine by MALDI-TOF/TOF-CID-MS/MS and LC-ESI-QqTOF-tandem mass spectrometry

    Science.gov (United States)

    Jahouh, Farid; Hou, Shu-jie; Kováč, Pavol; Banoub, Joseph H.

    2012-01-01

    We present herein an efficient mass spectrometric method for the localization of the glycation sites of a model neoglycoconjugate vaccine formed by a construct of the tetrasaccharide side chain of the Bacillus anthracis exosporium and the protein carrier bovine serum albumin. The glycoconjugate was digested with both trypsin and GluC V8 endoproteinases, and the digests were then analyzed by MALDI-TOF/TOF-CID-MS/MS and nano-LC-ESI-QqTOF-CID-MS/MS. The sequences of the unknown peptides analyzed by MALDI-TOF/TOF-CID-MS/MS, following digestion with the GluC V8 endoproteinase, allowed us to recognize three glycopeptides whose glycation occupancies were, respectively, on Lys 235, Lys 420, and Lys 498. Similarly, the same analysis was performed on the tryptic digests, which permitted us to recognize two glycation sites on Lys 100 and Lys 374. In addition, we have also used LC-ESI-QqTOF-CID-MS/MS analysis for the identification of the tryptic digests. However, this analysis identified a higher number of glycopeptides than would be expected from a glycoconjugate composed of a carbohydrate–protein ratio of 5.4:1, which would have resulted in glycation occupancies of 18 specific sites. This discrepancy was due to the large number of glycoforms formed during the synthetic carbohydrate–spacer–carrier protein conjugation. Likewise, the LC-ESI-QqTOF-MS/MS analysis of the GluC V8 digest also identified 17 different glycation sites on the synthetic glycoconjugate. PMID:22012665

  17. Lipid Peroxidation, Nitric Oxide Metabolites, and Their Ratio in a Group of Subjects with Metabolic Syndrome

    Directory of Open Access Journals (Sweden)

    Gregorio Caimi

    2014-01-01

    Full Text Available Our aim was to evaluate lipid peroxidation, expressed as thiobarbituric acid-reactive substances (TBARS, nitric oxide metabolites (nitrite + nitrate expressed as NOx, and TBARS/NOx ratio in a group of subjects with metabolic syndrome (MS. In this regard we enrolled 106 subjects with MS defined according to the IDF criteria, subsequently subdivided into diabetic (DMS and nondiabetic (NDMS and also into subjects with a low triglycerides/HDL-cholesterol (TG/HDL-C index or with a high TG/HDL-C index. In the entire group and in the four subgroups of MS subjects we found an increase in TBARS and NOx levels and a decrease in TBARS/NOx ratio in comparison with normal controls. Regarding all these parameters no statistical difference between DMS and NDMS was evident, but a significant increase in NOx was present in subjects with a high TG/HDL-C index in comparison with those with a low index. In MS subjects we also found a negative correlation between TBARS/NOx ratio and TG/HDL-C index. Considering the hyperactivity of the inducible NO synthase in MS, these data confirm the altered redox and inflammatory status that characterizes the MS and suggest a link between lipid peroxidation, inflammation, and insulin resistance, evaluated as TG/HDL-C index.

  18. Qualitative Analysis of E-Liquid Emissions as a Function of Flavor Additives Using Two Aerosol Capture Methods.

    Science.gov (United States)

    Eddingsaas, Nathan; Pagano, Todd; Cummings, Cody; Rahman, Irfan; Robinson, Risa; Hensel, Edward

    2018-02-13

    This work investigates emissions sampling methods employed for qualitative identification of compounds in e-liquids and their resultant aerosols to assess what capture methods may be sufficient to identify harmful and potentially harmful constituents present. Three popular e-liquid flavors (cinnamon, mango, vanilla) were analyzed using qualitative gas chromatography-mass spectrometry (GC-MS) in the un-puffed state. Each liquid was also machine-puffed under realistic-use flow rate conditions and emissions were captured using two techniques: filter pads and methanol impingers. GC-MS analysis was conducted on the emissions captured using both techniques from all three e-liquids. The e-liquid GC-MS analysis resulted in positive identification of 13 compounds from the cinnamon flavor e-liquid, 31 from mango, and 19 from vanilla, including a number of compounds observed in all e-liquid experiments. Nineteen compounds were observed in emissions which were not present in the un-puffed e-liquid. Qualitative GC-MS analysis of the emissions samples identify compounds observed in all three samples: e-liquid, impinge, and filter pads, and each subset thereof. A limited number of compounds were observed in emissions captured with impingers, but were not observed in emissions captured using filter pads; a larger number of compounds were observed on emissions collected from the filter pads, but not those captured with impingers. It is demonstrated that sampling methods have different sampling efficiencies and some compounds might be missed using only one method. It is recommended to investigate filter pads, impingers, thermal desorption tubes, and solvent extraction resins to establish robust sampling methods for emissions testing of e-cigarette emissions.

  19. Use of a PTR-MS for Multicomponent Flux Measurements over a Forest

    Energy Technology Data Exchange (ETDEWEB)

    Dommen, J; Spirig, C [FAL Reckenholz (Switzerland); Neftel, A [FAL Reckenholz (Switzerland); Thielmann, A [MPI Mainz (Georgia)

    2004-03-01

    A proton-transfer-reaction mass spectrometer was used to determine fluxes of biogenically emitted organic compounds over a forest canopy with the eddy covariance method. It was shown that several compounds can be simultaneously measured at a frequency high enough to calculate their fluxes. (author)

  20. Analysis of perchlorate in foods and beverages by ion chromatography coupled with tandem mass spectrometry (IC-ESI-MS/MS)

    Energy Technology Data Exchange (ETDEWEB)

    El Aribi, Houssain [Applied Biosystems/MDS Sciex, 71 Four Valley Drive, Concord, Ont., L4K 4V8 (Canada)]. E-mail: houssain.aribi@sciex.com; Le Blanc, Yves J.C. [Applied Biosystems/MDS Sciex, 71 Four Valley Drive, Concord, Ont., L4K 4V8 (Canada); Antonsen, Stephen [Dionex Canada Ltd., 1540 Cornwall Road, Oakville, Ont., L6J 7W5 (Canada); Sakuma, Takeo [Applied Biosystems/MDS Sciex, 71 Four Valley Drive, Concord, Ont., L4K 4V8 (Canada)

    2006-05-10

    A new IC-ESI-MS/MS method, with simple sample preparation procedure, has been developed for quantification and confirmation of perchlorate (ClO{sub 4} {sup -}) anions in water, fresh and canned food, wine and beer samples at low part-per-trillion (ng l{sup -1}) levels. To the best of our knowledge, this is the first time an analytical method is used for determination of perchlorate in wine and beer samples. The IC-ESI-MS/MS instrumentation consisted of an ICS-2500 ion chromatography (IC) system coupled to either an API 2000{sup TM} or an API 3200{sup TM} mass spectrometer. The IC-ESI-MS/MS system was optimized to monitor two pairs of precursor and fragment ion transitions, i.e., multiple reaction monitoring (MRM). All samples had oxygen-18 isotope labeled perchlorate internal standard (ISTD) added prior to extraction. Chlorine isotope ratio ({sup 35}Cl/{sup 37}Cl) was used as a confirmation tool. The transition of {sup 35}Cl{sup 16}O{sub 4} {sup -} (m/z 98.9) into {sup 35}Cl{sup 16}O{sub 3} {sup -} (m/z 82.9) was monitored for quantifying the main analyte; the transition of {sup 37}Cl{sup 16}O{sub 4} {sup -} (m/z 100.9) into {sup 37}Cl{sup 16}O{sub 3} {sup -} (m/z 84.9) was monitored for examining a proper isotopic abundance ratio of {sup 35}Cl/{sup 37}Cl; and the transition of {sup 35}Cl{sup 18}O{sub 4} {sup -} (m/z 107.0) into {sup 35}Cl{sup 18}O{sub 3} {sup -} (m/z 89.0) was monitored for quantifying the internal standard. The minimum detection limit (MDL) for this method in de-ionized water is 5 ng l{sup -1} (ppt) using the API 2000{sup TM} mass spectrometer and 0.5 ng l{sup -1} using the API 3200{sup TM} mass spectrometer. Over 350 food and beverage samples were analyzed mostly in triplicate. Except for four, all samples were found to contain measurable amounts of perchlorate. The levels found ranged from 5 ng l{sup -1} to 463.5 {+-} 6.36 {mu}g kg{sup -1} using MRM 98.9 {sup {yields}} 82.9 and 100 {mu}l injection.

  1. Interfacial photochemistry of biogenic surfactants: a major source of abiotic volatile organic compounds.

    Science.gov (United States)

    Brüggemann, Martin; Hayeck, Nathalie; Bonnineau, Chloé; Pesce, Stéphane; Alpert, Peter A; Perrier, Sébastien; Zuth, Christoph; Hoffmann, Thorsten; Chen, Jianmin; George, Christian

    2017-08-24

    Films of biogenic compounds exposed to the atmosphere are ubiquitously found on the surfaces of cloud droplets, aerosol particles, buildings, plants, soils and the ocean. These air/water interfaces host countless amphiphilic compounds concentrated there with respect to in bulk water, leading to a unique chemical environment. Here, photochemical processes at the air/water interface of biofilm-containing solutions were studied, demonstrating abiotic VOC production from authentic biogenic surfactants under ambient conditions. Using a combination of online-APCI-HRMS and PTR-ToF-MS, unsaturated and functionalized VOCs were identified and quantified, giving emission fluxes comparable to previous field and laboratory observations. Interestingly, VOC fluxes increased with the decay of microbial cells in the samples, indicating that cell lysis due to cell death was the main source for surfactants and VOC production. In particular, irradiation of samples containing solely biofilm cells without matrix components exhibited the strongest VOC production upon irradiation. In agreement with previous studies, LC-MS measurements of the liquid phase suggested the presence of fatty acids and known photosensitizers, possibly inducing the observed VOC production via peroxy radical chemistry. Up to now, such VOC emissions were directly accounted to high biological activity in surface waters. However, the results obtained suggest that abiotic photochemistry can lead to similar emissions into the atmosphere, especially in less biologically-active regions. Furthermore, chamber experiments suggest that oxidation (O 3 /OH radicals) of the photochemically-produced VOCs leads to aerosol formation and growth, possibly affecting atmospheric chemistry and climate-related processes, such as cloud formation or the Earth's radiation budget.

  2. Analysis of local-scale background concentrations of methane and other gas-phase species in the Marcellus Shale

    Directory of Open Access Journals (Sweden)

    J. Douglas Goetz

    2017-02-01

    Full Text Available The Marcellus Shale is a rapidly developing unconventional natural gas resource found in part of the Appalachian region. Air quality and climate concerns have been raised regarding development of unconventional natural gas resources. Two ground-based mobile measurement campaigns were conducted to assess the impact of Marcellus Shale natural gas development on local scale atmospheric background concentrations of air pollution and climate relevant pollutants in Pennsylvania. The first campaign took place in Northeastern and Southwestern PA in the summer of 2012. Compounds monitored included methane (CH4, ethane, carbon monoxide (CO, nitrogen dioxide, and Proton Transfer Reaction Mass Spectrometer (PTR-MS measured volatile organic compounds (VOC including oxygenated and aromatic VOC. The second campaign took place in Northeastern PA in the summer of 2015. The mobile monitoring data were analyzed using interval percentile smoothing to remove bias from local unmixed emissions to isolate local-scale background concentrations. Comparisons were made to other ambient monitoring in the Marcellus region including a NOAA SENEX flight in 2013. Local background CH4 mole fractions were 140 ppbv greater in Southwestern PA compared to Northeastern PA in 2012 and background CH4 increased 100 ppbv from 2012 to 2015. CH4 local background mole fractions were not found to have a detectable relationship between well density or production rates in either region. In Northeastern PA, CO was observed to decrease 75 ppbv over the three year period. Toluene to benzene ratios in both study regions were found to be most similar to aged rural air masses indicating that the emission of aromatic VOC from Marcellus Shale activity may not be significantly impacting local background concentrations. In addition to understanding local background concentrations the ground-based mobile measurements were useful for investigating the composition of natural gas emissions in the region.

  3. Direct ecosystem fluxes of volatile organic compounds from oil palms in South-East Asia

    Directory of Open Access Journals (Sweden)

    P. K. Misztal

    2011-09-01

    Full Text Available This paper reports the first direct eddy covariance fluxes of reactive biogenic volatile organic compounds (BVOCs from oil palms to the atmosphere using proton-transfer-reaction mass spectrometry (PTR-MS, measured at a plantation in Malaysian Borneo. At midday, net isoprene flux constituted the largest fraction (84 % of all emitted BVOCs measured, at up to 30 mg m−2 h−1 over 12 days. By contrast, the sum of its oxidation products methyl vinyl ketone (MVK and methacrolein (MACR exhibited clear deposition of 1 mg m−2 h−1, with a small average canopy resistance of 230 s m−1. Approximately 15 % of the resolved BVOC flux from oil palm trees could be attributed to floral emissions, which are thought to be the largest reported biogenic source of estragole and possibly also toluene. Although on average the midday volume mixing ratio of estragole exceeded that of toluene by almost a factor of two, the corresponding fluxes of these two compounds were nearly the same, amounting to 0.81 and 0.76 mg m−2 h−1, respectively. By fitting the canopy temperature and PAR response of the MEGAN emissions algorithm for isoprene and other emitted BVOCs a basal emission rate of isoprene of 7.8 mg m−2 h−1 was derived. We parameterise fluxes of depositing compounds using a resistance approach using direct canopy measurements of deposition. Consistent with Karl et al. (2010, we also propose that it is important to include deposition in flux models, especially for secondary oxidation products, in order to improve flux predictions.

  4. Theoretical emission line ratios for [Fe III] and [Fe VII] applicable to the optical and infrared spectra of gaseous nebulae.

    Science.gov (United States)

    Keenan, F P; Aller, L H; Ryans, R S; Hyung, S

    2001-08-14

    Recent calculations of electron impact excitation rates and Einstein A-coefficients for transitions among the 3d(6) levels of Fe III and among the 3d(2) levels of Fe VII are used to derive theoretical emission line ratios applicable to the optical and infrared spectra of gaseous nebulae. Results for [Fe III] are generated for electron temperatures T(e) = 7,000-20,000 K and densities N(e) = 10(2)-10(8) cm(-3), whereas those for [Fe VII] are provided for T(e) = 10,000-30,000 K and N(e) = 10(2)-10(8) cm(-3). The theoretical line ratios are significantly different in some instances from earlier calculations and resolve discrepancies between theory and observation found for the planetary nebulae IC 4997 and NGC 7027.

  5. LC-MS (/MS) in clinical toxicology screening methods.

    Science.gov (United States)

    Viette, Véronique; Hochstrasser, Denis; Fathi, Marc

    2012-01-01

    Toxicological screening is the analysis of biological samples to detect and identify unknown compounds. The high selectivity and sensitivity of liquid chromatography (LC) coupled to mass spectrometry (MS) or tandem mass spectrometry (MS/MS) technology provide an attractive alternative to the current methods (LC-UV, GC/MS, etc.). For these reasons, an increasing number of applications are being published. This paper is a brief overview of LC-MS(/MS) screening methods developed for clinical toxicology in recent years. Various sample treatments, chromatographic separations and detection by mass spectrometry can be combined to obtain screening methods adapted to the constraints and needs of clinical toxicology laboratories. Currently the techniques are in the hands of specialists, mainly in academic institutions. However, the evolution in technology should allow application of these techniques as a tool in toxicology laboratories, thus allowing a more widespread exploitation of their potential.

  6. Electronics for processing of data from a double collector isotopic ratio mass spectrometer

    International Nuclear Information System (INIS)

    Handu, V.K.

    1979-01-01

    The output data available from the mass spectrometer type MS-660 developed in the mass spectrometry section of Technical Physics Division of the Bhabha Atomic Research Centre, Bombay, for the determination of H/D ratios in liquid/gas sample consist of uncompensated mass 3 and mass 2 signals. After the mass 3 signal has been compensated for H 3 + formation, the on-line ratio of compensated mass 3 to mass 2 is calculated, displayed, and then printed on a printer for record. The electronic compensation circuit, the discrete voltage-to-frequency (V/F) converter circuit, the ratio calculating system using V/F converters, and a digital interface system for Hindustan Teleprinter to print out the ratios are explained. Results obtained on mass spectrometer MS-660 are presented. (auth.)

  7. Determination of Algorithm Parallelism in NP Complete Problems for Distributed Architectures

    Science.gov (United States)

    1990-03-05

    12 structure STACK declare OpenStack (S-.NODE **TopPtr) -+TopPtrI FlushStack(S.-NODE **TopPtr) -*TopPtr PushOnStack(S-.NODE **TopPtr, ITEM *NewltemPtr...OfCoveringSets, CoveringSets, L, Best CoverTime, Vertex, Set3end SCND ADT B.26 structure STACKI declare OpenStack (S-NODE **TopPtr) -+TopPtr FlushStack(S

  8. Comparative effectiveness of primary tumor resection in patients with stage IV colon cancer.

    Science.gov (United States)

    Alawadi, Zeinab; Phatak, Uma R; Hu, Chung-Yuan; Bailey, Christina E; You, Y Nancy; Kao, Lillian S; Massarweh, Nader N; Feig, Barry W; Rodriguez-Bigas, Miguel A; Skibber, John M; Chang, George J

    2017-04-01

    Although the safety of combination chemotherapy without primary tumor resection (PTR) in patients with stage IV colon cancer has been established, questions remain regarding a potential survival benefit with PTR. The objective of this study was to compare mortality rates in patients who had colon cancer with unresectable metastases who did and did not undergo PTR. An observational cohort study was conducted among patients with unresectable metastatic colon cancer identified from the National Cancer Data Base (2003-2005). Multivariate Cox regression analyses with and without propensity score weighting (PSW) were performed to compare survival outcomes. Instrumental variable analysis, using the annual hospital-level PTR rate as the instrument, was used to account for treatment selection bias. To account for survivor treatment bias, in situations in which patients might die soon after diagnosis from different reasons, a landmark method was used. In the total cohort, 8641 of 15,154 patients (57%) underwent PTR, and 73.8% of those procedures (4972 of 6735) were at landmark. PTR was associated with a significant reduction in mortality using Cox regression (hazard ratio [HR], 0.45; 95% confidence interval [CI], 0.44-0.47) or PSW (HR, 0.46; 95% CI, 0. 44-0.49). However, instrumental variable analysis revealed a much smaller effect (relative mortality rate, 0.91; 95% CI, 0.87-0.96). Although a smaller benefit was observed with the landmark method using Cox regression (HR, 0.6; 95% CI, 0.55-0.64) and PSW (HR, 0.59; 95% CI, 0.54-0.64), instrumental variable analysis revealed no survival benefit (relative mortality rate, 0.97; 95% CI, 0.87-1.06). Among patients with unresectable metastatic colon cancer, after adjustment for confounder effects, PTR was not associated with improved survival compared with systemic chemotherapy; therefore, routine noncurative PTR is not recommended. Cancer 2017;123:1124-1133. © 2016 American Cancer Society. © 2016 American Cancer Society.

  9. Analysis of acrylamide by LC-MS/MS and GC-MS in processed Japanese foods.

    Science.gov (United States)

    Ono, H; Chuda, Y; Ohnishi-Kameyama, M; Yada, H; Ishizaka, M; Kobayashi, H; Yoshida, M

    2003-03-01

    Acrylamide concentrations in processed foods (63 samples covering 31 product types) from Japan were analysed by LC-MS/MS and GC-MS methods. The limit of detection and limit of quantification of acrylamide were 0.2 ng x ml(-1) (6 fmol) and 0.8 ng x ml(-1) (22 fmol), respectively, by LC-MS/MS, and those of 2,3-dibromopropionamide derived from acrylamide were 12 ng x ml(-1) (52 fmol) and 40 ng x ml(-1) (170 fmol), respectively, by GC-MS. Repeatability given as RSD was 1000 microg x kg(-1). The concentrations in non-whole potato-based snacks, rice crackers processed by grilling or frying, and candied sweet potatoes were lower compared with those in the potato crisps and the whole potato-based fried snacks. One of the whole potato-based fried snacks, however, showed low acrylamide concentration (instant precooked noodles and won-tons were <100 microg x kg(-1) with only one exception. Roasted barley grains for 'Mugi-cha' tea contained 200-600 microg x kg(-1) acrylamide.

  10. Preliminary study of urine metabolism in type two diabetic patients based on GC-MS

    OpenAIRE

    Zhang, Ning; Geng, Fang; Hu, Zhong-Hua; Liu, Bin; Wang, Ye-Qiu; Liu, Jun-Cen; Qi, Yong-Hua; Li, Li-Jing

    2016-01-01

    Objective: Comparative study of type 2 diabetes and healthy controls by metabolomics methods to explore the pathogenesis of Type II diabetes. Methods: Gas chromatography - mass spectrometry (GC-MS) with a variety of multivariate statistical analysis methods to the healthy control group 58 cases, 68 cases of Type II diabetes group were analyzed. Chromatographic conditions: DB-5MS column; the carrier gas He; flow rate of 1 mL·min-1, the injection volume 1 uL; split ratio is 100: 1. MS condition...

  11. Current role of ICP-MS in clinical toxicology and forensic toxicology: a metallic profile.

    Science.gov (United States)

    Goullé, Jean-Pierre; Saussereau, Elodie; Mahieu, Loïc; Guerbet, Michel

    2014-08-01

    As metal/metalloid exposure is inevitable owing to its omnipresence, it may exert toxicity in humans. Recent advances in metal/metalloid analysis have been made moving from flame atomic absorption spectrometry and electrothermal atomic absorption spectrometry to the multi-elemental inductively coupled plasma (ICP) techniques as ICP atomic emission spectrometry and ICP-MS. ICP-MS has now emerged as a major technique in inorganic analytical chemistry owing to its flexibility, high sensitivity and good reproducibility. This in depth review explores the ICP-MS metallic profile in human toxicology. It is now routinely used and of great importance, in clinical toxicology and forensic toxicology to explore biological matrices, specifically whole blood, plasma, urine, hair, nail, biopsy samples and tissues.

  12. Can we trust mass spectrometry for determination of arsenic peptides in plants: comparison of LC-ICP-MS and LC-ES-MS/ICP-MS with XANES/EXAFS in analysis of Thunbergia alata.

    Science.gov (United States)

    Bluemlein, Katharina; Raab, Andrea; Meharg, Andrew A; Charnock, John M; Feldmann, Jörg

    2008-04-01

    The weakest step in the analytical procedure for speciation analysis is extraction from a biological material into an aqueous solution which undergoes HPLC separation and then simultaneous online detection by elemental and molecular mass spectrometry (ICP-MS/ES-MS). This paper describes a study to determine the speciation of arsenic and, in particular, the arsenite phytochelatin complexes in the root from an ornamental garden plant Thunbergia alata exposed to 1 mg As L(-1) as arsenate. The approach of formic acid extraction followed by HPLC-ES-MS/ICP-MS identified different As(III)-PC complexes in the extract of this plant and made their quantification via sulfur (m/z 32) and arsenic (m/z 75) possible. Although sulfur sensitivity could be significantly increased when xenon was used as collision gas in ICP-qMS, or when HR-ICP-MS was used in medium resolution, the As:S ratio gave misleading results in the identification of As(III)-PC complexes due to the relatively low resolution of the chromatography system in relation to the variety of As-peptides in plants. Hence only the parallel use of ES-MS/ICP-MS was able to prove the occurrence of such arsenite phytochelatin complexes. Between 55 and 64% of the arsenic was bound to the sulfur of peptides mainly as As(III)(PC(2))(2), As(III)(PC(3)) and As(III)(PC(4)). XANES (X-ray absorption near-edge spectroscopy) measurement, using the freshly exposed plant root directly, confirmed that most of the arsenic is trivalent and binds to S of peptides (53% As-S) while 38% occurred as arsenite and only 9% unchanged as arsenate. EXAFS data confirmed that As-S and As-O bonds occur in the plants. This study confirms, for the first time, that As-peptides can be extracted by formic acid and chromatographically separated on a reversed-phase column without significant decomposition or de-novo synthesis during the extraction step.

  13. Inductively coupled plasma-mass spectrometry for elemental analysis and isotope ratio determinations in individual organic compounds separated by gas chromatography

    International Nuclear Information System (INIS)

    Chong, N.S.; Houk, R.S.

    1987-01-01

    A gas chromatograph (GC) with a packed column was interfaced to an inductively coupled plasma-mass spectrometer (ICP-MS) to yield atomic mass spectra from volatile organic compounds. Atomization of injected compounds was nearly complete and independent of molecular structure, so that elemental ratios could be determined. Detection limits were in the range 0.001 to 400 ng s -1 , depending on the ionization energy of the element and its abundance in the background spectrum. The relative standard deviation of measured isotope ratios varied from 0.4% for Br (i.e., a ratio close to unity) to 18% for N (a very large ratio). Thus, GC-ICP-MS provides elemental and isotope ratio information that is complementary to the molecular information derived from GC-MS with conventional ionization methods

  14. Response surface methodology based optimization of diesel–n-butanol –cotton oil ternary blend ratios to improve engine performance and exhaust emission characteristics

    International Nuclear Information System (INIS)

    Atmanlı, Alpaslan; Yüksel, Bedri; İleri, Erol; Deniz Karaoglan, A.

    2015-01-01

    Highlights: • RSM based optimization for optimum blend ratio of diesel fuel, n-butanol and cotton oil was done. • 65.5 vol.% diesel fuel, 23.1 vol.% n-butanol and 11.4 vol.% cotton oil (DnBC) was determined. • DnBC decreased brake torque, brake power, BTE and BMEP, while increased BSFC. • DnBC decreased NO x , CO and HC emissions. - Abstract: Many studies declare that 20% biodiesel is the optimum concentration for biodiesel–diesel fuel blends to improve performance. The present work focuses on finding diesel fuel, n-butanol, and cotton oil optimum blend ratios for diesel engine applications by using the response surface method (RSM). Experimental test fuels were prepared by choosing 7 different concentrations, where phase decomposition did not occur in the phase diagram of −10 °C. Experiments were carried out at full load conditions and the constant speed (2200 rpm) of maximum brake torque to determine engine performance and emission parameters. According to the test results of the engine, optimization was done by using RSM considering engine performance and exhaust emissions parameters, to identify the rates of concentrations of components in the optimum blend of three. Confirmation tests were employed to compare the output values of concentrations that were identified by optimization. The real experiment results and the R 2 actual values that show the relation between the outputs from the optimizations and real experiments were determined in high accordance. The optimum component concentration was determined as 65.5 vol.% diesel, 23.1 vol.% n-butanol and 11.4 vol.% cotton oil (DnBC). According to engine performance tests brake torque, brake power, BTE and BMEP of DnBC decreased while BSFC increased compared to those of diesel fuel. NO x , CO and HC emissions of DnBC drastically decreased as 11.33%, 45.17% and 81.45%, respectively

  15. Metabolite profiling with HPLC-ICP-MS as a tool for in vivo characterization of imaging probes.

    Science.gov (United States)

    Boros, Eszter; Pinkhasov, Omar R; Caravan, Peter

    2018-01-01

    Current analytical methods for characterizing pharmacokinetic and metabolic properties of positron emission tomography (PET) and single photon emission computed tomography (SPECT) probes are limited. Alternative methods to study tracer metabolism are needed. The study objective was to assess the potential of high performance liquid chromatography - inductively coupled plasma - mass spectrometry (HPLC-ICP-MS) for quantification of molecular probe metabolism and pharmacokinetics using stable isotopes. Two known peptide-DOTA conjugates were chelated with nat Ga and nat In. Limit of detection of HPLC-ICP-MS for 69 Ga and 115 In was determined. Rats were administered 50-150 nmol of Ga- and/or In-labeled probes, blood was serially sampled, and plasma analyzed by HPLC-ICP-MS using both reverse phase and size exclusion chromatography. The limits of detection were 0.16 pmol for 115 In and 0.53 pmol for 69 Ga. Metabolites as low as 0.001 %ID/g could be detected and transchelation products identified. Simultaneous administration of Ga- and In-labeled probes allowed the determination of pharmacokinetics and metabolism of both probes in a single animal. HPLC-ICP-MS is a robust, sensitive and radiation-free technique to characterize the pharmacokinetics and metabolism of imaging probes.

  16. Prediction of fetal lung maturity using the lecithin/sphingomyelin (L/S) ratio analysis with a simplified sample preparation, using a commercial microtip-column combined with mass spectrometric analysis.

    Science.gov (United States)

    Kwak, Ho-Seok; Chung, Hee-Jung; Choi, Young Sik; Min, Won-Ki; Jung, So Young

    2015-07-01

    Fetal lung maturity is estimated using the lecithin/sphingomyelin ratio (L/S ratio) in amniotic fluid and it is commonly measured with thin-layer chromatography (TLC). The TLC method is time consuming and technically difficult; however, it is widely used because there is no alternative. We evaluated a novel method for measuring the L/S ratio, which involves a tip-column with a cation-exchange resin and mass spectrometry. Phospholipids in the amniotic fluid were extracted using methanol and chloroform. Choline-containing phospholipids such as lecithin and sphingomyelin were purified by passing them through the tip-column. LC-MS/MS and MALDI-TOF were used to directly analyze the purified samples. The L/S ratio by mass spectrometry was calculated from the sum peak intensity of the six lecithin, and that of sphingomyelin 34:1. In 20 samples, the L/S ratio determined with TLC was significantly correlated with that obtained by LC-MS/MS and MALDI-TOF. There was a 100% concordance between the L/S ratio by TLC and that by LC-MS/MS (kappa value=1.0). The concordance between the L/S ratio by TLC and that by MALDI-TOF was also 100% (kappa value=1.0). Our method provides a faster, simpler, and more reliable assessment of fetal lung maturity. The L/S ratio measured by LC-MS/MS and MALDI-TOF offers a compelling alternative method to traditional TLC. Copyright © 2015 Elsevier B.V. All rights reserved.

  17. Fine Structure in Proton Emission from the Deformed 141g.sHo and 141mHo

    International Nuclear Information System (INIS)

    Karny, M.; Rykaczewski, Krzysztof Piotr; Grzywacz, R.; Batchelder, J.C.; Bingham, C.R.; Goodin, C. T.; Gross, Carl J.; Hamilton, J.H.; Korgul, A.; Krolas, W.; Liddick, S. N.; Li, K.; Maier, Karl; Mazzocchi, C.; Piechaczek, A.; Shapira, Dan; Simpson, D.; Tantawy, M.N.; Winger, J.A.; Yu, Chang-Hong; Zganjar, E. F.

    2007-01-01

    Fine structure in proton emission from the deformed states 141g.s Ho (T 1/2 = 4.1 ms) and 141 mHo (T 1/2 = 7.4 (micro)s) has been discovered at Oak Ridge by detecting fusion evaporation residues with the Recoil Mass Spectrometer, Si-detectors and digital signal processing electronics. The branching ratios to the first 2 + excited state in 140 Dy were measured to be I p g.s. (2 + ) = 0.9±0.1% and I p m (2 + ) = 1.7±0.5%. A comparison of the available calculations to the experimental values calls for further development of the theoretical models

  18. Demographic characteristics of MS patients in Poland's upper Silesia region.

    Science.gov (United States)

    Pierzchala, Krystyna; Adamczyk-Sowa, Monika; Dobrakowski, Pawel; Kubicka-Baczyk, Katarzyna; Niedziela, Natalia; Sowa, Pawel

    2015-05-01

    In Poland, no national registry of MS patients has yet been introduced. So far, no demographic studies have been conducted in patients with MS in Upper Silesia. The aim of the present study was to evaluate, for the first time, a selected demographic and clinical parameters in MS patients from the Upper Silesia region and compare these characteristics with previously published data from other regions of Poland. 640 patients with clinically defined MS, were prospectively and randomly selected for the study. Social, socio-economic, and demographic data were obtained through a questionnaire study. All subjects performed a self-assessment of their health condition using EQ-5D and EQ-VAS version questionnaires. The ratio of women to men was 2.18. The average age of onset was 29.6 ± 11.1 years; the disease duration was 7.9 ± 4.5 years. The relapsing-remitting form of MS was diagnosed in 73.12%. In 71.25% the onset was monofocal and in 28.75% multifocal disease onset was observed. Among the studied population 339 (52.97%) patients were still employed. A mean EQ-VAS score of 66.11 ± 20.12 was calculated. Results from our study identify for the first time the demographic and clinical characteristics of the Upper Silesia MS population.

  19. Trace gas emissions from burning Florida wetlands

    Science.gov (United States)

    Cofer, Wesley R.; Levine, Joel S.; Winstead, Edward L.; Lebel, Peter J.; Koller, Albert M.; Hinkle, C. Ross

    1990-02-01

    Measurements of biomass burn-produced trace gases are presented that were obtained using a helicopter at low altitudes above burning Florida wetlands on November 9, 1987, and from both helicopter and light-aircraft samplings on November 7, 1988. Carbon dioxide (CO2) normalized emission ratios (ΔX/ΔCO2; V/V; where X is trace gas) for carbon monoxide (CO), hydrogen (H2), methane (CH4), total nonmethane hydrocarbons (TNMHC), and nitrous oxide (N2O) were obtained over burning graminoid wetlands consisting primarily of Spartina bakeri and Juncus roemerianus. Some interspersed scrub oak (Quercus spp) and saw palmetto (Screnoa repens) were also burned. No significant differences were observed in the emission ratios determined for these gases from samples collected over flaming, mixed, and smoldering phases of combustion during the 1987 fire. Combustion-categorized differences in emission ratios were small for the 1988 fire. Combustion efficiency was relatively good (low emission ratios for reduced gases) for both fires. We believe that the consistently low emission ratios were a unique result of graminoid wetlands fires, in which the grasses and rushes (both small-size fuels) burned rapidly down to standing water and were quickly extinguished. Consequently, the efficiency of the combustion was good and the amount and duration of smoldering combustion was greatly diminished.

  20. Two-dimensional HPLC coupled to ICP-MS and electrospray ionisation (ESI)-MS/MS for investigating the bioavailability in vitro of arsenic species from edible seaweed

    Energy Technology Data Exchange (ETDEWEB)

    Garcia-Sartal, Cristina; Barciela-Alonso, Maria del Carmen; Bermejo-Barrera, Pilar [University of Santiago de Compostela, Department of Analytical Chemistry, Nutrition and Bromatology, Faculty of Chemistry, Santiago de Compostela (Spain); Taebunpakul, Sutthinun [LGC Limited, Teddington, Middlesex (United Kingdom); Imperial College of Science, Technology and Medicine, South Kensington, Department of Materials, London (United Kingdom); National Institute of Metrology (Thailand), Pathumthani (Thailand); Stokes, Emma; Goenaga-Infante, Heidi [LGC Limited, Teddington, Middlesex (United Kingdom)

    2012-04-15

    Edible seaweed consumption is a route of exposure to arsenic. However, little attention has been paid to estimate the bioaccessibility and/or bioavailability of arsenosugars in edible seaweed and their possible degradation products during gastrointestinal digestion. This work presents first use of combined inductively coupled plasma mass spectroscopy (ICP-MS) with electrospray ionization tandem mass spectrometry (ESI-MS/MS) with two-dimensional HPLC (size exclusion followed by anion exchange) to compare the qualitative and quantitative arsenosugars speciation of different edible seaweed with that of their bioavailable fraction as obtained using an in vitro gastrointestinal digestion procedure. Optimal extraction conditions for As species from four seaweed namely kombu, wakame, nori and sea lettuce were selected as a compromise between As extraction efficiency and preservation of compound identity. For most investigated samples, the use of ammonium acetate buffer as extractant and 1 h sonication in a water bath followed by HPLC-ICP-MS resulted in 40-61% of the total As to be found in the buffered aqueous extract, of which 86-110% was present as arsenosugars (glycerol sugar, phosphate sugar and sulfonate sugar for wakame and kombu and glycerol sugar and phosphate sugar for nori). The exception was sea lettuce, for which the arsenosugar fraction (glycerol sugar, phosphate sugar) only comprised 44% of the total extracted As. Interestingly, the ratio of arsenobetaine and dimethylarsinic acid to arsenosugars in sea lettuce extracts seemed higher than that for the rest of investigated samples. After in vitro gastrointestinal digestion, approximately 11-16% of the total As in the solid sample was found in the dialyzates with arsenosugars comprising 93-120% and 41% of the dialyzable As fraction for kombu, wakame, nori and sea lettuce, respectively. Moreover, the relative As species distribution in seaweed-buffered extracts and dialyzates was found to be very similar

  1. Selenium speciation analysis of Misgurnus anguillicaudatus selenoprotein by HPLC-ICP-MS and HPLC-ESI-MS/MS

    Science.gov (United States)

    Analytical methods for selenium (Se) speciation were developed using high performance liquid chromatography (HPLC) coupled to either inductively coupled plasma mass spectrometry (ICP-MS) or electrospray ionization tandem mass spectrometry (ESI-MS/MS). Separations of selenomethionine (Se-Met) and sel...

  2. MassSieve: Panning MS/MS peptide data for proteins

    OpenAIRE

    Slotta, Douglas J.; McFarland, Melinda A.; Markey, Sanford P.

    2010-01-01

    We present MassSieve, a Java-based platform for visualization and parsimony analysis of single and comparative LC-MS/MS database search engine results. The success of mass spectrometric peptide sequence assignment algorithms has led to the need for a tool to merge and evaluate the increasing data set sizes that result from LC-MS/MS-based shotgun proteomic experiments. MassSieve supports reports from multiple search engines with differing search characteristics, which can increase peptide sequ...

  3. Determination of trace element concentrations and stable lead, uranium and thorium isotope ratios by quadrupole-ICP-MS in NORM and NORM-polluted sample leachates

    Energy Technology Data Exchange (ETDEWEB)

    Mas, J.L., E-mail: ppmasb@us.es [Dpto. Fisica Aplicada I, EPS, Universidad de Sevilla, 41012 Sevilla (Spain); Villa, M. [Servicio de Radioisotopos, Centro de Investigacion, Tecnologia e Innovacion (CITIUS), Universidad de Sevilla, Avda. Reina Mercedes 4b, 41012 Sevilla (Spain); Dpto. Fisica Aplicada II, ETS de Arquitectura, Universidad de Sevilla, Avda. Reina Mercedes 2, 41012 Sevilla (Spain); Hurtado, S. [Servicio de Radioisotopos, Centro de Investigacion, Tecnologia e Innovacion (CITIUS), Universidad de Sevilla, Avda. Reina Mercedes 4b, 41012 Sevilla (Spain); Garcia-Tenorio, R. [Dpto. Fisica Aplicada II, ETS de Arquitectura, Universidad de Sevilla, Avda. Reina Mercedes 2, 41012 Sevilla (Spain)

    2012-02-29

    Highlights: Black-Right-Pointing-Pointer Polluted sediment and NORM samples. Black-Right-Pointing-Pointer An efficient yet fast process allowing multi-parametric determinations in <3 days. Black-Right-Pointing-Pointer Trace element concentrations, Pb, Th and U isotope ratios with a single instrument. - Abstract: This work focuses on the monitoring of the potential pollution in scenarios that involve NORM-related industrial activities (environmental or in-door scenarios). The objective was to develop a method to determine extent and origin of the contamination, suitable for monitoring (i.e. simple, fast and economical) and avoiding the use of too many different instruments. It is presented a radiochemical method that allows the determination of trace element concentrations and {sup 206}Pb/{sup 207}Pb/{sup 208}Pb, {sup 238}U/{sup 234}U and {sup 232}Th/{sup 230}Th isotope ratios using a single sample aliquot and a single instrument (ICP-QMS). Eichrom UTEVA{sup Registered-Sign} extraction chromatography minicolumns were used to separate uranium and thorium in sample leachates. Independent ICP-MS determinations of uranium and thorium isotope ratios were carried out afterwards. Previously a small aliquot of the leachate was used for the determination of trace element concentrations and lead isotope ratios. Several radiochemical arrangements were tested to get maximum performances and simplicity of the method. The performances of the method were studied in terms of chemical yields of uranium and thorium and removal of the potentially interfering elements. The established method was applied to samples from a chemical industry and sediments collected in a NORM-polluted scenario. The results obtained from our method allowed us to infer not only the extent, but also the sources of the contamination in the area.

  4. Measurement of stable isotope ratio of organic carbon in water samples

    International Nuclear Information System (INIS)

    Fujii, Toshihiro; Otsuki, Akira

    1977-01-01

    A new method for the measurement of stable isotope ratios was investigated and applied to organic carbon's isotope ratio measurements in water samples. A few river water samples from Tsuchiura city were tested. After the wet oxidation of organic carbons to carbon dioxide in a sealed ampoule, the isotope ratios were determined with the gas chromatograph-quadrupole mass spectrometer combined with a total organic carbon analyser, under the dynamic conditions. The GC-MS had been equipped with the multiple ion detector-digital integrator system. The ion intensities at m/e 44 and 45 were simultaneously measured at a switching rate of 1 ms. The measurements with carbon dioxide acquired from sodium carbonate (53 μg) gave the isotope ratios with the variation coefficient of 0.62%. However, the variation coefficients obtained from organic carbons in natural water samples were 2 to 3 times as high as that from sodium carbonate. This method is simple and rapid and may be applied to various fields especially in biology and medicine. (auth.)

  5. Implications of Fast Reactor Transuranic Conversion Ratio

    International Nuclear Information System (INIS)

    Piet, Steven J.; Hoffman, Edward A.; Bays, Samuel E.

    2010-01-01

    Theoretically, the transuranic conversion ratio (CR), i.e. the transuranic production divided by transuranic destruction, in a fast reactor can range from near zero to about 1.9, which is the average neutron yield from Pu239 minus 1. In practice, the possible range will be somewhat less. We have studied the implications of transuranic conversion ratio of 0.0 to 1.7 using the fresh and discharge fuel compositions calculated elsewhere. The corresponding fissile breeding ratio ranges from 0.2 to 1.6. The cases below CR=1 ('burners') do not have blankets; the cases above CR=1 ('breeders') have breeding blankets. The burnup was allowed to float while holding the maximum fluence to the cladding constant. We graph the fuel burnup and composition change. As a function of transuranic conversion ratio, we calculate and graph the heat, gamma, and neutron emission of fresh fuel; whether the material is 'attractive' for direct weapon use using published criteria; the uranium utilization and rate of consumption of natural uranium; and the long-term radiotoxicity after fuel discharge. For context, other cases and analyses are included, primarily once-through light water reactor (LWR) uranium oxide fuel at 51 MWth-day/kg-iHM burnup (UOX-51). For CR 1, heat, gamma, and neutron emission decrease with recycling. The uranium utilization exceeds 1%, especially as all the transuranic elements are recycled. exceeds 1%, especially as all the transuranic elements are recycled. At the system equilibrium, heat and gamma vary by somewhat over an order of magnitude as a function of CR. Isotopes that dominate heat and gamma emission are scattered throughout the actinide chain, so the modest impact of CR is unsurprising. Neutron emitters are preferentially found among the higher actinides, so the neutron emission varies much stronger with CR, about three orders of magnitude.

  6. Radioactive air emissions notice of construction portable temporary radioactive air emission units - August 1998; FINAL

    International Nuclear Information System (INIS)

    FRITZ, D.W.

    1999-01-01

    single categorical license that identifies limits and conditions of operations for similar multipurpose temporary and or portable emission units. The DOE-RL will submit annually to the WDOH a report summarizing the log books maintained on the individual PTRAEUs that are used during the reporting period. The report will supply information needed to ensure compliance with the condition of operations. The NOC includes a general description of the three types of PTRAEUs, tracking mechanisms, emissions control systems, and radioactivity handling limits (RHLs) for the PTR4EUs. The NOC is based on hypothetical data to demonstrate how emission estimates could be calculated. Tracking will be performed and monitoring will be conducted for compliance with both federal and state regulations. Type I units will use a single isotope based on a calculated RHL (source term) to determine emissions, dose, and monitoring requirements. Type I1 and 111 units will use field data and process knowledge to determine emissions, dose, and monitoring requirements. New PTRAEUs that conform to any of the three types of PTRAEUs described in this application will be added to the next annual report after the units are placed in service. New PTRAEUs, which do not conform to any of the three types of PTRAEUs described in this application, will require approval on an individual basis by the WDOH before startup

  7. Biomass Burning: Major Uncertainties, Advances, and Opportunities

    Science.gov (United States)

    Yokelson, R. J.; Stockwell, C.; Veres, P. R.; Hatch, L. E.; Barsanti, K. C.; Liu, X.; Huey, L. G.; Ryerson, T. B.; Dibb, J. E.; Wisthaler, A.; Müller, M.; Alvarado, M. J.; Kreidenweis, S. M.; Robinson, A. L.; Toon, O. B.; Peischl, J.; Pollack, I. B.

    2014-12-01

    Domestic and open biomass burning are poorly-understood, major influences on Earth's atmosphere composed of countless individual fires that (along with their products) are difficult to quantify spatially and temporally. Each fire is a minimally-controlled complex phenomenon producing a diverse suite of gases and aerosols that experience many different atmospheric processing scenarios. New lab, airborne, and space-based observations along with model and algorithm development are significantly improving our knowledge of biomass burning. Several campaigns provided new detailed emissions profiles for previously undersampled fire types; including wildfires, cooking fires, peat fires, and agricultural burning; which may increase in importance with climate change and rising population. Multiple campaigns have better characterized black and brown carbon and used new instruments such as high resolution PTR-TOF-MS and 2D-GC/TOF-MS to improve quantification of semi-volatile precursors to aerosol and ozone. The aerosol evolution and formation of PAN and ozone, within hours after emission, have now been measured extensively. The NASA DC-8 sampled smoke before and after cloud-processing in two campaigns. The DC-8 performed continuous intensive sampling of a wildfire plume from the source in California to Canada probing multi-day aerosol and trace gas aging. Night-time plume chemistry has now been measured in detail. Fire inventories are being compared and improved, as is modeling of mass transfer between phases and sub-grid photochemistry for global models.

  8. Numerical investigation of ethanol fuelled HCCI engine using stochastic reactor model. Part 2: Parametric study of performance and emissions characteristics using new reduced ethanol oxidation mechanism

    International Nuclear Information System (INIS)

    Maurya, Rakesh Kumar; Akhil, Nekkanti

    2016-01-01

    Highlights: • Newly developed reduced ethanol mechanism (47 species and 272 reactions) used. • Engine maps over wide range are developed for performance and emissions parameters. • HCCI operating range increases with compression ratio & decreases with engine speed. • Maximum combustion efficiency up to 99% and thermal efficiency up to 50% is achieved. • Maximum N_2O emission found up to 2.7 ppm and lower load have higher N_2O emission. - Abstract: Ethanol fuelled homogenous charge compression ignition engine offers a better alternative to tackle the problems of achieving higher engine efficiency and lower emissions using renewable fuel. Present study computationally investigates the HCCI operating range of ethanol at different compression ratios by varying inlet air temperature and engine speed using stochastic reactor model. A newly developed reduced ethanol oxidation mechanism with NO_x having 47 species and 272 reactions is used for simulation. HCCI operating range for compression ratios 17, 19 and 21 are investigated and found to be increasing with compression ratio. Simulations are conducted for engine speeds ranging from 1000 to 3000 rpm at different intake temperatures (range 365–465 K). Parametric study of combustion and emission characteristics is conducted and engine maps are developed at most efficient inlet temperatures. HCCI operating range is defined using combustion efficiency (>85%) and maximum pressure rise rate (<5 MPa/ms). In HCCI operating range, higher efficiency is found at higher engine loads and lower engine speeds. Emission characteristics of species (NO_x, N_2O, CO, CH_4, C_2H_4, C_2H_6, CH_3CHO, and HCHO) found in significant amount is also analysed for ethanol fulled HCCI engine. Emission maps for different species are presented and discussed for wide range of speed and load conditions. Some of unregulated species such as aldehydes are emitted in significantly higher quantities from ethanol fuelled HCCI engine at higher load

  9. Air pollution from motor vehicle emissions

    International Nuclear Information System (INIS)

    Petrushevska, Ljubica

    1996-01-01

    This paper presents some aspects of air pollution from motor vehicle emissions as: characteristic primary and secondary pollutants, dependence of the motor vehicle emission from the engine type; the relationship of typical engine emission and performance to air-fuel ratio, transport of pollutants from mobile sources of emissions, as well as some world experiences in the control approaches for exhaust emissions. (author)

  10. Potassium Stable Isotopic Compositions Measured by High-Resolution MC-ICP-MS

    Science.gov (United States)

    Morgan, Leah E.; Lloyd, Nicholas S.; Ellam, Robert M.; Simon, Justin I.

    2012-01-01

    Potassium isotopic (K-41/K-39) compositions are notoriously difficult to measure. TIMS measurements are hindered by variable fractionation patterns throughout individual runs and too few isotopes to apply an internal spike method for instrumental mass fractionation corrections. Internal fractionation corrections via the K-40/K-39 ratio can provide precise values but assume identical K-40/K-39 ratios (e.g. 0.05% (1sigma) in [1]); this is appropriate in some cases (e.g. identifying excess K-41) but not others (e.g., determining mass fractionation effects and metrologically traceable isotopic abundances). SIMS analyses have yielded measurements with 0.25% precisions (1sigma) [2]. ICP-MS analyses are significantly affected by interferences from molecular species such as Ar-38H(+) and Ar-40H(+) and instrument mass bias. Single collector ICP-MS instruments in "cold plasma" mode have yielded uncertainties as low as 2% (1sigma, e.g. [3]). Although these precisions may be acceptable for some concentration determinations, they do not resolve isotopic variation in terrestrial materials. Here we present data from a series of measurements made on the Thermo Scientific NEPTUNE Plus multi-collector ICP-MS that demonstrate the ability to make K-41/K-39 ratio measurements with 0.07% precisions (1sigma). These data, collected on NIST K standards, indicate the potential for MC-ICP-MS measurements to look for K isotopic variations at the sub-permil level. The NEPTUNE Plus can sufficiently resolve 39K and 41K from the interfering 38ArH+ and 40ArH+ peaks in wet cold plasma and high-resolution mode. Measurements were made on small but flat, interference-free, plateaus (ca. 50 ppm by mass width for K-41). Although ICP-MS does not yield accurate K-41/K-39 values due to significant instrumental mass fractionation (ca. 6%), this bias can be sufficiently stable over the time required for several measurements so that relative K-41/K-39 values can be precisely determined via sample

  11. Relapsing-Remitting MS (RRMS)

    Medline Plus

    Full Text Available ... Area Donate Donate Search v What Is MS? Definition of MS What Causes MS? Who Gets MS? ... Support Personal Stories d What Is MS? d Definition of MS Myelin Immune-Mediated Disease T Cells ...

  12. Removal of acidic interferences in multi-pesticides residue analysis of fruits using modified magnetic nanoparticles prior to determination via ultra-HPLC-MS/MS

    International Nuclear Information System (INIS)

    Qi, Peipei; Wang, Zhiwei; Yang, Guiling; Wang, Xinquan; Shang, Chunqing; Xu, Hao; Wang, Xiangyun; Zhang, Hu; Wang, Qiang

    2015-01-01

    The authors describe magnetite (Fe 3 O 4 ) nanoparticles modified with 3-(N,N-diethylamino) propyltrimethoxysilane (Fe 3 O 4 -PSA NPs) for use as a sorbent for dispersive solid phase extraction of pesticide residues. The Fe 3 O 4 -PSA NPs were prepared by silanizing Fe 3 O 4 NPs and modifying them with 3-(N,N-diethylamino) propyltrimethoxysilane. Field-emission scanning electron microscopy, FTIR and zeta potential measurements were employed to characterize the modified NPs. They were then used as an adsorbent to remove acidic interferences (such as malic acid and succinic acid), which are major interferences in LC-MS/MS analysis in causing ion suppression in the MS spectra of pesticides. In addition, graphitized carbon black (GCB) was used as an adsorbent to eliminate interferences by pigments. The use of Fe 3 O 4 -PSA NPs can replace time-consuming centrifugation as used in the so-called QuEChERS (quick, easy, cheap, effective, rugged and safe) method. This improvement is particularly significant in high-throughput analysis. Following the optimization of the quantities of Fe 3 O 4 -PSA NPs and GCB, the method was applied to the determination of 56 pesticides in (spiked) fruits (apple, kiwi, orange and pear) by ultra-HPLC-MS/MS. The analytical ranges typically extend from 1 to 200 ng∙mL −1 , and recoveries range from 60.2 to 130 % at different concentrations of all four kinds of fruits. The LOQs for the pesticides are 10 ng∙kg −1 , which makes the method a viable tool for pesticide monitoring in fruits. (author)

  13. Metabolic profiling of roots of liquorice (Glycyrrhiza glabra) from different geographical areas by ESI/MS/MS and determination of major metabolites by LC-ESI/MS and LC-ESI/MS/MS.

    Science.gov (United States)

    Montoro, Paola; Maldini, Mariateresa; Russo, Mariateresa; Postorino, Santo; Piacente, Sonia; Pizza, Cosimo

    2011-02-20

    Liquid chromatography electrospray mass spectrometry (LC-ESI/MS) has been applied to the full characterization of saponins and phenolics in hydroalcoholic extracts of roots of liquorice (Glycyrrhiza glabra). Relative quantitative analyses of the samples with respect to the phenolic constituents and to a group of saponins related to glycyrrhizic acid were performed using LC-ESI/MS. For the saponin constituents, full scan LC-MS/MS fragmentation of the protonated (positive ion mode) or deprotonated (negative ion mode) molecular species generated diagnostic fragment ions that provided information concerning the triterpene skeleton and the number and nature of the substituents. On the basis of the specific fragmentation of glycyrrhizic acid, an LC-MS/MS method was developed in order to quantify the analyte in the liquorice root samples. Chinese G. glabra roots contained the highest levels of glycyrrhizic acid, followed by those from Italy (Calabria). Copyright © 2010 Elsevier B.V. All rights reserved.

  14. Intensity ratio among Ne-like FeXVII n=3-2 transitions

    International Nuclear Information System (INIS)

    Morita, Shigeru; Oishi, Tetsutarou; Murakami, Izumi; Goto, Motoshi; Huang, Xianli; Zhang, Hongming

    2016-01-01

    Radial profiles of FeXVII 3s-2p and 3d-2p transitions emitted in wavelength range of 15-17A have been observed in Large Helical Device (LHD). The Chord-integrated radial profiles are converted into radial emissivity profile by means of Abel inversion. The emissivity ratios among FeXVII n=3-2 transitions calculated from the radial emissivity profile are compared with calculation based on a collisional-radiative (CR) model developed for Fe ions. The result reasonably confirms the effect of electron temperature and density on the emissivity ratios. However, the emissivity of 3C (2p"53d "1P_1 → 2p"6) transition is obviously lower than the prediction from the CR model. This discrepancy is consistent with measurements in the solar corona and other laboratory plasmas. (author)

  15. The influence of laser pulse duration and energy on ICP-MS signal intensity, elemental fractionation, and particle size distribution in NIR fs-LA-ICP-MS

    Science.gov (United States)

    Diwakar, Prasoon K.; Harilal, Sivanandan S.; LaHaye, Nicole L.; Hassanein, Ahmed; Kulkarni, Pramod

    2015-01-01

    Laser parameters, typically wavelength, pulse width, irradiance, repetition rate, and pulse energy, are critical parameters which influence the laser ablation process and thereby influence the LA-ICP-MS signal. In recent times, femtosecond laser ablation has gained popularity owing to the reduction in fractionation related issues and improved analytical performance which can provide matrix-independent sampling. The advantage offered by fs-LA is due to shorter pulse duration of the laser as compared to the phonon relaxation time and heat diffusion time. Hence the thermal effects are minimized in fs-LA. Recently, fs-LA-ICP-MS demonstrated improved analytical performance as compared to ns-LA-ICP-MS, but detailed mechanisms and processes are still not clearly understood. Improvement of fs-LA-ICP-MS over ns-LA-ICP-MS elucidates the importance of laser pulse duration and related effects on the ablation process. In this study, we have investigated the influence of laser pulse width (40 fs to 0.3 ns) and energy on LA-ICP-MS signal intensity and repeatability using a brass sample. Experiments were performed in single spot ablation mode as well as rastering ablation mode to monitor the Cu/Zn ratio. The recorded ICP-MS signal was correlated with total particle counts generated during laser ablation as well as particle size distribution. Our results show the importance of pulse width effects in the fs regime that becomes more pronounced when moving from femtosecond to picosecond and nanosecond regimes. PMID:26664120

  16. Low predictability of anthropometric indicators of obesity in metabolic syndrome (MS) risks among elderly women.

    Science.gov (United States)

    Chu, Fu-Ling; Hsu, Chung-Huei; Jeng, Chii

    2012-01-01

    While diagnostic criteria for MS may vary depending on ethnicity, obesity remains a key risk factor in its development. In Taiwan, the incidence of obesity and MS among women has been increasing; however cut-off values for defining obesity for the diagnosis of MS among different groups of women have not been clearly established. The goal of this research was to examine the suitability of various anthropometric indicators of obesity in predicting the presence of MS criteria and to determine appropriate cut-off values of these indicators for women of different age and menstrual status. The sample was derived from the 2002 "Taiwan Three High Prevalence Survey" database. Women were divided into three groups based on age and menstrual status. Receiver-operating characteristic (ROC) curves was applied to the anthropometric indicators of obesity including, body mass index (BMI), waist circumference (WC), waist-to-hip ratio (WHR), waist-to-height ratio (WHtR), to ascertain its value in predicting MS. 2848 cases were included. It was found that most MS component values were worse with age and following menopause. Obesity indicators showed poor predictability for MS risks in post-menopausal women over 65 years, but good predictability in women under 65 years; our study revealed the following as ideal cut-off values for non-menopausal female: WHtRrisks in women over the age of 65, and cut-off values for obesity indicators need to be further reduced in non-menopausal women. Copyright © 2012 Elsevier Ireland Ltd. All rights reserved.

  17. Analysis of poly-beta-hydroxybutyrate in environmental samples by GC-MS/MS.

    Science.gov (United States)

    Elhottová, D; Tríska, J; Petersen, S O; Santrůcková, H

    2000-05-01

    Application of gas chromatography-mass spectrometry (GC-MS) can significantly improve trace analyses of compounds in complex matrices from natural environments compared to gas chromatography only. A GC-MS/MS technique for determination of poly-beta-hydroxybutyrate (PHB), a bacterial storage compound, has been developed and used for analysis of two soils stored for up to 319 d, fresh samples of sewage sludge, as well as a pure culture of Bacillus megaterium. Specific derivatization of beta-hydroxybutyrate (3-OH C4:0) PHB monomer units by N-tert-butyl-dimethylsilyl-N-methyltrifluoracetamide (MTBSTFA) improved chromatographic and mass spectrometric properties of the analyte. The diagnostic fragmentation scheme of the derivates tert-butyldimethylsilyl ester and ether of beta-hydroxybutyric acid (MTBSTFA-HB) essential for the PHB identification was shown. The ion trap MS was used, therefore the scan gave the best sensitivity and with MS/MS the noise decreased, so the S/N was better and also with second fragmentation the amount of ions increased compared to SIM. The detection limit for MTBSTFA-HB by GC-MS/MS was about 10(-13) g microL(-1) of injected volume, while by GC (FID) and GC-MS (scan) it was around 10(-10) g microL(-1) of injected volume. Sensitivity of GC-MS/MS measurements of PHB in arable soil and activated sludge samples was down to 10 pg of PHB g(-1) dry matter. Comparison of MTBSTFA-HB detection in natural soil sample by GC (FID), GC-MS (scan) and by GC-MS/MS demonstrated potentials and limitations of the individual measurement techniques.

  18. Quantification of amygdalin in nonbitter, semibitter, and bitter almonds (Prunus dulcis) by UHPLC-(ESI)QqQ MS/MS.

    Science.gov (United States)

    Lee, Jihyun; Zhang, Gong; Wood, Elizabeth; Rogel Castillo, Cristian; Mitchell, Alyson E

    2013-08-14

    Amygdalin is a cynaogenic diglucoside responsible for the bitterness of almonds. Almonds display three flavor phenotypes, nonbitter, semibitter, and bitter. Herein, the amygdalin content of 20 varieties of nonbitter, semibitter, and bitter almonds from four primary growing regions of California was determined using solid-phase extraction and ultrahigh-pressure liquid chromatography electrospray triple-quadrupole mass spectrometry (UHPLC-(ESI)QqQ MS/MS). The detection limit for this method is ≤ 0.1 ng/mL (3 times the signal-to-noise ratio) and the LOQ is 0.33 ng/mL (10 times the signal-to-noise ratio), allowing for the reliable quantitation of trace levels of amygdalin in nonbitter almonds (0.13 mg/kg almond). Results indicate that amygdalin concentrations for the three flavor phenotypes were significantly different (p almonds are 63.13 ± 57.54, 992.24 ± 513.04, and 40060.34 ± 7855.26 mg/kg, respectively. Levels of amygdalin ranged from 2.16 to 157.44 mg/kg in nonbitter, from 523.50 to 1772.75 mg/kg in semibitter, and from 33006.60 to 53998.30 mg/kg in bitter almonds. These results suggest that phenotype classification may be achieved on the basis of amygdalin levels. Growing region had a statistically significant effect on the amygdalin concentration in commercial varieties (p < 0.05).

  19. Comparative metabolomics analysis for the compatibility and incompatibility of kansui and licorice with different ratios by UHPLC-QTOF/MS and multivariate data analysis.

    Science.gov (United States)

    Shen, Juan; Pu, Zong-Jin; Kai, Jun; Kang, An; Tang, Yu-Ping; Shang, Li-Li; Zhou, Gui-Sheng; Zhu, Zhen-Hua; Shang, Er-Xin; Li, Shao-Ping; Cao, Yu-Jie; Tao, Wei-Wei; Su, Shu-Lan; Zhang, Li; Zhou, Huiping; Qian, Da-Wei; Duan, Jin-Ao

    2017-07-01

    Kansui, the root of Euphorbia kansui T.N. Liou ex T.P. Wang (Euphorbiaceae), is a well-known poisonous traditional Chinese medicine (TCM). However, many monographs of TCM indicated that it cannot be co-used with licorice, as kansui-licorice is a typical "eighteen incompatible" medicaments. Our previous studies have indicated that kansui was effective in treating malignant pleural effusion (MPE), and the efficacy could be weakened by the co-use of licorice, even causing serious toxicity at the given ratio. Nevertheless, the actual mechanisms of their dosage-toxicity-efficacy relationship need to be well clarified. The present study aimed to investigate the effect of individual and combined use of kansui and licorice on MPE rats, and explain the underlying mechanisms from a metabolomic perspective. Urine samples were analyzed by ultra-high-performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry (UHPLC-QTOF/MS). Partial least-squares discriminate analysis (PLS-DA) models were built to evaluate the interaction between kansui and licorice. Seven potential biomarkers contribute to the separation of model group and control group were tentatively identified. And selenoamino acid metabolism and nicotinate and nicotinamide metabolism with the impact-value 0.31 and 0.24, respectively, were filtered out as the most important metabolic pathways. Kansui and kansui-licorice at a ratio of 4:1 can treat MPE rats by adjusting abnormal metabolic pathways to the normal state, while it may have opposite result with kansui-licorice 1:4. The different influences to the two metabolic pathways may partially explain the dosage-toxicity-efficacy relationship of kansui-licorice with different ratios. The results could offer valuable insights into the compatibility property changes for the two herbs. Copyright © 2017 Elsevier B.V. All rights reserved.

  20. OUTFLOW AND HOT DUST EMISSION IN HIGH-REDSHIFT QUASARS

    International Nuclear Information System (INIS)

    Wang, Huiyuan; Xing, Feijun; Wang, Tinggui; Zhou, Hongyan; Zhang, Kai; Zhang, Shaohua

    2013-01-01

    Correlations of hot dust emission with outflow properties are investigated, based on a large z ∼ 2 non-broad absorption line quasar sample built from the Wide-field Infrared Survey and the Sloan Digital Sky Survey data releases. We use the near-infrared slope and the infrared to UV luminosity ratio to indicate the hot dust emission relative to the emission from the accretion disk. In our luminous quasars, these hot dust emission indicators are almost independent of the fundamental parameters, such as luminosity, Eddington ratio and black hole mass, but moderately dependent on the blueshift and asymmetry index (BAI) and FWHM of C IV lines. Interestingly, the latter two correlations dramatically strengthen with increasing Eddington ratio. We suggest that, in high Eddington ratio quasars, C IV regions are dominated by outflows so the BAI and FWHM (C IV) can reliably reflect the general properties and velocity of outflows, respectively. In low Eddington ratio quasars, on the other hand, C IV lines are primarily emitted by virialized gas so the BAI and FWHM (C IV) become less sensitive to outflows. Therefore, the correlations for the highest Eddington ratio quasars are more likely to represent the true dependence of hot dust emission on outflows and the correlations for the entire sample are significantly diluted by the low Eddington ratio quasars. Our results show that an outflow with a large BAI or velocity can double the hot dust emission on average. We suggest that outflows either contain hot dust in themselves or interact with the dusty interstellar medium or torus

  1. Provenancing Flower Bulbs by Analytical Fingerprinting: Convallaria Majalis

    Directory of Open Access Journals (Sweden)

    Saskia M. van Ruth

    2015-01-01

    Full Text Available The origin of agricultural products is gaining in appreciation while often hard to determine for various reasons. Geographical origin may be resolved using a combination of chemical and physical analytical technologies. In the present case of Lily of the Valley (Convallaria majalis rhizomes, we investigated an exploratory set of material from The Netherlands, three other European (EU countries and China. We show that the geographical origin is correlated to patterns of stable isotope ratios (isotope fingerprints and volatile organic carbon (VOC compounds (chemical fingerprints. These fingerprints allowed clear distinction using exploratory and supervised statistics. Isotope ratio mass spectrometry of 12C/13C, 14N/15N and 16O/18O isotopes separated materials from Europe and China successfully. The VOC patterns measured by Proton Transfer Reaction Mass Spectrometry (PTR-MS allowed distinction of three groups: material from The Netherlands, the other EU countries and China. This knowledge is expected to help developing a systematic and efficient analytical tool for authenticating the origin of flower bulbs.

  2. Enteric methane emissions from German pigs

    DEFF Research Database (Denmark)

    Dämmgen, Ulrich; Schulz, Joachim; Klausing, Heinrich Kleine

    2012-01-01

    Methane emissions from enteric fermentation of pigs are object of emission reporting. Hitherto they were treated as part of the energy balance of pigs, in accordance with IPCC guidance documents. They were calculated from the gross energy intake rate and a constant methane conversion ratio....... Meanwhile numerous experimental data on methane emissions from enteric fermentation is available in Germany and abroad; the results are compiled in this work. These results also allow for a description of transformation processes in the hind gut and a subsequent establishment of models that relate emissions...... to feed and performance data. The model by Kirchgeßner et al. (1995) is based on German experimental data and reflects typical national diet compositions. It is used to quantify typical emissions and methane conversion ratios. The results agree with other experimental findings at home and abroad...

  3. Effects of stabilizer ratio on photoluminescence properties of sol-gel ZnO nano-structured thin films

    International Nuclear Information System (INIS)

    Boudjouan, F.; Chelouche, A.; Touam, T.; Djouadi, D.; Khodja, S.; Tazerout, M.; Ouerdane, Y.; Hadjoub, Z.

    2015-01-01

    Nanostructured ZnO thin films with different molar ratios of MEA to zinc acetate (0.5, 1.0, 1.5 and 2.0) have been deposited on glass substrates by a sol–gel dip coating technique. X-ray diffraction, Scanning Electron Microscopy, UV–visible spectrophotometry and photoluminescence spectroscopy have been employed to investigate the effect of MEA stabilizer ratio on structural, morphological, absorbance and emission properties of the ZnO thin films. Diffraction patterns have shown that all the films are polycrystalline and exhibit a wurtzite hexagonal structure. The c axis orientation has been enhanced with increasing stabilizer ratio. SEM micrographs have revealed that the morphology of the ZnO films depend on stabilizer ratio. The UV–visible absorption spectra have demonstrated that the optical absorption is affected by stabilizer ratio. The photoluminescence spectra have indicated one ultraviolet and two visible emission bands (green and red), while band intensities are found to be dependent on stabilizer ratio. ZnO thin films deposited at MEA ratio of 1.0 show the highest UV emission while the minimum UV emission intensity is observed in thin films deposited at ratio of 0.5 and the maximum green has been recorded for films deposited at MEA ratio of 2.0. - Highlight: • c axis orientation increases with increasing MEA ratio. • The increase of MEA ration from 0.5 to 1.0 enhances greatly the UV emission. • The larger I UV /I visible is obtained for the MEA to Zn ratio of 1:1. • The MEA ratio of 0.5 favors the formation of large density of V zn . • The MEA ratio of 2.0 increases the V o density

  4. Determination of trace elements in seawater by air-flow injection/ICP-MS with chelating resin preconcentration

    International Nuclear Information System (INIS)

    Lee, Kyue-Hyung; Ohshima, Mitsuko; Motomizu, Shoji

    2002-01-01

    Multielement determination of major to trace metals in a deep seawater malt was accomplished by inductively coupled plasma-mass spectrometry (ICP-MS) together with inductively coupled plasma-atomic emission spectrometry (ICP-AES). Major elements, such as Na, K, Mg, and Ca, were measured by ICP-AES and normal continuos nebulization ICP-MS after sample dilution by 10 3 -10 6 fold. Fifteen trace elements in the concentrated metal solutions pretreated with cation-exchange resin or chelating resin could be simultaneously determined by air-flow injection/ICP-mass spectrometry (AFI/ICP-MS). Since the injection volume for AFI/ICP-MS was 25 μl, final samples volumes less than 500 μl were enough for several replicate measurements. Three different preconcentration methods assisted with AFI/ICP-MS were examined and could be successfully applied to a deep seawater malt. The analytical results of rate earth elements (REEs) and Co, Ni, Cu, Zn, Cd, and Pb obtained by AFI/ICP-MS coupled with disk filtration method using iminodiacetate (IDA)-type chelating resin were favorably agreed with the data obtained by AFI/ICP-MS coupled with column preconcentration method using chitosan-based chelating resin. (author)

  5. CO line ratios in molecular clouds: the impact of environment

    Science.gov (United States)

    Peñaloza, Camilo H.; Clark, Paul C.; Glover, Simon C. O.; Klessen, Ralf S.

    2018-04-01

    Line emission is strongly dependent on the local environmental conditions in which the emitting tracers reside. In this work, we focus on modelling the CO emission from simulated giant molecular clouds (GMCs), and study the variations in the resulting line ratios arising from the emission from the J = 1-0, J = 2-1, and J = 3-2 transitions. We perform a set of smoothed particle hydrodynamics simulations with time-dependent chemistry, in which environmental conditions - including total cloud mass, density, size, velocity dispersion, metallicity, interstellar radiation field (ISRF), and the cosmic ray ionization rate (CRIR) - were systematically varied. The simulations were then post-processed using radiative transfer to produce synthetic emission maps in the three transitions quoted above. We find that the cloud-averaged values of the line ratios can vary by up to ±0.3 dex, triggered by changes in the environmental conditions. Changes in the ISRF and/or in the CRIR have the largest impact on line ratios since they directly affect the abundance, temperature, and distribution of CO-rich gas within the clouds. We show that the standard methods used to convert CO emission to H2 column density can underestimate the total H2 molecular gas in GMCs by factors of 2 or 3, depending on the environmental conditions in the clouds.

  6. Optimization of Ultrasound-Assisted Extraction, HPLC and UHPLC-ESI-Q-TOF-MS/MS Analysis of Main Macamides and Macaenes from Maca (Cultivars of Lepidium meyenii Walp

    Directory of Open Access Journals (Sweden)

    Shu-Xiao Chen

    2017-12-01

    Full Text Available Ultrasound-assisted extraction (UAE, using petroleum ether as the solvent, was systematically applied to extract main macamides and macaenes from Maca hypocotyls. Extraction yield was related with four variables, including ratio of solution to solid, extraction temperature, extraction time, and extraction power. On the basis of response surface methodology (RSM, the optimal conditions were determined to be the ratio of solution to solid as 10:1 (mL/g, the extraction temperature of 40 °C, the extraction time of 30 min, and the extraction power of 200 W. Based on the optimal extraction method of UAE, the total contents of ten main macamides and two main macaenes of Maca cultivated in twenty different areas of Tibet were analyzed by HPLC and UHPLC-ESI-Q-TOF-MS/MS. This study indicated that UAE was able to effectively extract macamides alkaloids from Maca hypocotyls. Quantitative analysis showed that geographical origins, not ecotypes, played a more important role on the accumulation of active macamides in Maca.

  7. Optimization of Ultrasound-Assisted Extraction, HPLC and UHPLC-ESI-Q-TOF-MS/MS Analysis of Main Macamides and Macaenes from Maca (Cultivars of Lepidium meyenii Walp).

    Science.gov (United States)

    Chen, Shu-Xiao; Li, Ke-Ke; Pubu, Duoji; Jiang, Si-Ping; Chen, Bin; Chen, Li-Rong; Yang, Zhen; Ma, Chao; Gong, Xiao-Jie

    2017-12-10

    Ultrasound-assisted extraction (UAE), using petroleum ether as the solvent, was systematically applied to extract main macamides and macaenes from Maca hypocotyls. Extraction yield was related with four variables, including ratio of solution to solid, extraction temperature, extraction time, and extraction power. On the basis of response surface methodology (RSM), the optimal conditions were determined to be the ratio of solution to solid as 10:1 (mL/g), the extraction temperature of 40 °C, the extraction time of 30 min, and the extraction power of 200 W. Based on the optimal extraction method of UAE, the total contents of ten main macamides and two main macaenes of Maca cultivated in twenty different areas of Tibet were analyzed by HPLC and UHPLC-ESI-Q-TOF-MS/MS. This study indicated that UAE was able to effectively extract macamides alkaloids from Maca hypocotyls. Quantitative analysis showed that geographical origins, not ecotypes, played a more important role on the accumulation of active macamides in Maca.

  8. Emission ratio and isotopic signatures of molecular hydrogen emissions from tropical biomass burning

    NARCIS (Netherlands)

    Haumann, F.A.; Batenburg, A.M.; Pieterse, G.; Gerbig, C.; Krol, M.C.; Rockmann, T.

    2013-01-01

    In this study, we identify a biomass-burning signal in molecular hydrogen (H-2) over the Amazonian tropical rainforest. To quantify this signal, we measure the mixing ratios of H-2 and several other species as well as the H-2 isotopic composition in air samples that were collected in the BARCA

  9. Cannabinoids determination in oral fluid by SPME-GC/MS and UHPLC-MS/MS and its application on suspected drivers.

    Science.gov (United States)

    Anzillotti, Luca; Castrignanò, Erika; Strano Rossi, Sabina; Chiarotti, Marcello

    2014-12-01

    The confirmation of Δ9-tetrahydrocannabinol (THC) in oral fluid (OF) is an important issue for assessing Driving Under the Influence of Drugs (DUID). The aim of this research was to develop a highly sensitive method with minimal sample pre-treatment suitable for the analysis of small OF volumes (100 μL) for the confirmation of cannabinoids in DUID cases. Two methods were compared for the confirmation of THC in residual OF samples, obtained from a preliminary on-site screening with commercial devices. An ultra high performance LC-MS (UHPLC-MS/MS) method and an SPME-GC/MS method were hence developed. 100 μL of the residual mixture OF/preservative buffer or neat OF was simply added to 10 μL of THC-D3 (1 μg/mL) and submitted to the two different analyses: A - direct injection of 10 μL in UHPLC-MS/MS in positive electrospray ionisation (ESI) mode and B - sampling for 30 min with SPME (100 μm polydimethylsiloxane or PDMS fibre) and direct injection by desorption of the fibre in the GC injection port. The lowest limit of detection (LLOD) of THC was 2 ng/mL in UHPLC-MS/MS and 0.5 ng/mL in SPME-GC/MS. In addition, cannabidiol (CBD) and cannabinol (CBN) could be detected in GC/MS equipment at 2 ng/mL, whilst in UHPLC-MS/MS the LLOD was 20 ng/mL. Both methods were applied to 70 samples coming from roadside tests. By SPME-GC/MS analysis, THC was confirmed in 42 samples, whilst CBD was detected in 21 of them, along with CBN in 14 samples. THC concentrations ranged from traces below the lowest limit of quantification or LLOQ (2 ng/mL) up to 690 ng/mL. Copyright © 2014 Forensic Science Society. Published by Elsevier Ireland Ltd. All rights reserved.

  10. Software ion scan functions in analysis of glycomic and lipidomic MS/MS datasets.

    Science.gov (United States)

    Haramija, Marko

    2018-03-01

    Hardware ion scan functions unique to tandem mass spectrometry (MS/MS) mode of data acquisition, such as precursor ion scan (PIS) and neutral loss scan (NLS), are important for selective extraction of key structural data from complex MS/MS spectra. However, their software counterparts, software ion scan (SIS) functions, are still not regularly available. Software ion scan functions can be easily coded for additional functionalities, such as software multiple precursor ion scan, software no ion scan, and software variable ion scan functions. These are often necessary, since they allow more efficient analysis of complex MS/MS datasets, often encountered in glycomics and lipidomics. Software ion scan functions can be easily coded by using modern script languages and can be independent of instrument manufacturer. Here we demonstrate the utility of SIS functions on a medium-size glycomic MS/MS dataset. Knowledge of sample properties, as well as of diagnostic and conditional diagnostic ions crucial for data analysis, was needed. Based on the tables constructed with the output data from the SIS functions performed, a detailed analysis of a complex MS/MS glycomic dataset could be carried out in a quick, accurate, and efficient manner. Glycomic research is progressing slowly, and with respect to the MS experiments, one of the key obstacles for moving forward is the lack of appropriate bioinformatic tools necessary for fast analysis of glycomic MS/MS datasets. Adding novel SIS functionalities to the glycomic MS/MS toolbox has a potential to significantly speed up the glycomic data analysis process. Similar tools are useful for analysis of lipidomic MS/MS datasets as well, as will be discussed briefly. Copyright © 2017 John Wiley & Sons, Ltd.

  11. Determination of toxins involved in ciguatera fish poisoning in the Pacific by LC/MS.

    Science.gov (United States)

    Yogi, Kentaro; Sakugawa, Satsuki; Oshiro, Naomasa; Ikehara, Tsuyoshi; Sugiyama, Kiminori; Yasumoto, Takeshi

    2014-01-01

    Ciguatera fish poisoning is the most extensive and difficult to control of the seafood poisonings. To facilitate monitoring of fish toxicity, toxin profiles were investigated by an LC/MS/MS method using 14 reference toxins on eight representative species of fish collected in four different areas of the Pacific. Snappers and groupers from Okinawa contained ciguatoxin-1B (CTX1B) and two deoxy congeners at variable but species-specific ratios, while red snapper, Lutjanus bohar, from Minamitorishima, and amberjack, Seriola dumerili, from Hawaii, contained both CTX1B-type and CTX3C-type toxins. Spotted knifejaw, Oplegnathus punctatus, from Okinawan waters, contained mainly CTX4A and CTX4B, but the same species caught at Miyazaki was contaminated primarily with the CTX3C-type toxins. Otherwise, the toxin profiles were consistently species-specific in fish collected from various locations around Okinawa over 20 years. The LC/MS/MS and mouse bioassay results agreed well, indicating the LC/MS/MS method is a promising alternative to the mouse bioassay. Pure CTX1B and CTX3C were prepared for use in future LC/MS/MS analysis.

  12. Emission ratio and isotopic signatures of molecular hydrogen emissions from tropical biomass burning

    NARCIS (Netherlands)

    Haumann, F.A.; Batenburg, A.M.; Pieterse, G.; Gerbig, C; Krol, M.C.; Röckmann, T.

    2013-01-01

    In this study, we identify a biomass-burning signal in molecular hydrogen (H2) over the Amazonian tropical rainforest. To quantify this signal, we measure the mixing ratios of H2 and several other species as well as the H2 isotopic composition in air samples that were collected in the BARCA (Balanço

  13. Simultaneous quantification of seven hippocampal neurotransmitters in depression mice by LC-MS/MS.

    Science.gov (United States)

    Huang, Fei; Li, Jia; Shi, Hai-Lian; Wang, Ting-ting; Muhtar, Wahaf; Du, Min; Zhang, Bei-bei; Wu, Hui; Yang, Li; Hu, Zhi-bi; Wu, Xiao-jun

    2014-05-30

    There is no method available to simultaneously detect GABA, Glu, Epi, NE, DA, 5-HT and 5-HIAA in mouse hippocampus. A rapid and sensitive LC-MS/MS method has been developed for simultaneously measuring seven neurotransmitters in mouse hippocampus. The analytes were detected in positive mode with multiple reaction monitoring (MRM) and the procedure was completed in less than 9min. This method exhibited excellent linearity for all of the analytes with regression coefficients higher than 0.99, and showed good intra- and inter-day precisions (RSDneurotransmitters in a mouse depression model induced by successive methylprednisolone injections. The results indicated that this depression model was closely associated with the decreased level of Epi (p=0.002) and elevated ratio of 5-HIAA/5-HT (p=0.01), which has never been reported elsewhere. Compared with previous methods, current approach is more convenient without any pre-column derivatization of the analytes but enhances detectability with incremental neurotransmitter profile and shortens detection time. This work represents the first accurate simultaneous determination of seven neurotransmitters in the mouse depression model induced by methylprednisolone. The reliable method will benefit the research of neurological diseases with the altered neurotransmitter profile in brain. Copyright © 2014 Elsevier B.V. All rights reserved.

  14. MASPECTRAS: a platform for management and analysis of proteomics LC-MS/MS data

    Directory of Open Access Journals (Sweden)

    Rader Robert

    2007-06-01

    Full Text Available Abstract Background The advancements of proteomics technologies have led to a rapid increase in the number, size and rate at which datasets are generated. Managing and extracting valuable information from such datasets requires the use of data management platforms and computational approaches. Results We have developed the MAss SPECTRometry Analysis System (MASPECTRAS, a platform for management and analysis of proteomics LC-MS/MS data. MASPECTRAS is based on the Proteome Experimental Data Repository (PEDRo relational database schema and follows the guidelines of the Proteomics Standards Initiative (PSI. Analysis modules include: 1 import and parsing of the results from the search engines SEQUEST, Mascot, Spectrum Mill, X! Tandem, and OMSSA; 2 peptide validation, 3 clustering of proteins based on Markov Clustering and multiple alignments; and 4 quantification using the Automated Statistical Analysis of Protein Abundance Ratios algorithm (ASAPRatio. The system provides customizable data retrieval and visualization tools, as well as export to PRoteomics IDEntifications public repository (PRIDE. MASPECTRAS is freely available at http://genome.tugraz.at/maspectras Conclusion Given the unique features and the flexibility due to the use of standard software technology, our platform represents significant advance and could be of great interest to the proteomics community.

  15. Emissions from forest fires near Mexico City

    Directory of Open Access Journals (Sweden)

    R. J. Yokelson

    2007-11-01

    Full Text Available The emissions of NOx (defined as NO (nitric oxide + NO2 (nitrogen dioxide and hydrogen cyanide (HCN, per unit amount of fuel burned, from fires in the pine forests that dominate the mountains surrounding Mexico City (MC are about 2 times higher than normally observed for forest burning. The ammonia (NH3 emissions are about average for forest burning. The upper limit for the mass ratio of NOx to volatile organic compounds (VOC for these MC-area mountain fires was ~0.38, which is similar to the NOx/VOC ratio in the MC urban area emissions inventory of 0.34, but much larger than the NOx/VOC ratio for tropical forest fires in Brazil (~0.068. The nitrogen enrichment in the fire emissions may be due to deposition of nitrogen-containing pollutants in the outflow from the MC urban area. This effect may occur worldwide wherever biomass burning coexists with large urban areas (e.g. the tropics, southeastern US, Los Angeles Basin. The molar emission ratio of HCN to carbon monoxide (CO for the mountain fires was 0.012±0.007, which is 2–9 times higher than widely used literature values for biomass burning. The ambient molar ratio HCN/CO in the MC-area outflow is about 0.003±0.0003. Thus, if only mountain fires emit significant amounts of HCN, these fires may be contributing about 25% of the CO production in the MC-area (~98–100 W and 19–20 N. Comparing the PM10/CO and PM2.5/CO mass ratios in the MC Metropolitan Area emission inventory (0.0115 and 0.0037 to the PM1/CO mass ratio for the mountain fires (0.133 then suggests that these fires could produce as much as ~79–92% of the primary fine particle mass generated in the MC-area. Considering both the uncertainty in the HCN/CO ratios and secondary aerosol formation in the urban and fire emissions implies that about 50±30% of the "aged" fine particle mass in the March 2006 MC-area outflow could be from these fires.

  16. Energy intensity, life-cycle greenhouse gas emissions, and economic assessment of liquid biofuel pipelines.

    Science.gov (United States)

    Strogen, Bret; Horvath, Arpad; Zilberman, David

    2013-12-01

    Petroleum fuels are predominantly transported domestically by pipelines, whereas biofuels are almost exclusively transported by rail, barge, and truck. As biofuel production increases, new pipelines may become economically attractive. Location-specific variables impacting pipeline viability include construction costs, availability and costs of alternative transportation modes, electricity prices and emissions (if priced), throughput, and subsurface temperature. When transporting alcohol or diesel-like fuels, pipelines have a lower direct energy intensity than rail, barge, and trucks if fluid velocity is under 1 m/s for 4-inch diameter pipelines and 2 m/s for 8-inch or larger pipelines. Across multiple hypothetical state-specific scenarios, profit-maximizing design velocities range from 1.2 to 1.9 m/s. In costs and GHG emissions, optimized pipelines outperform trucks in each state and rail and barge in most states, if projected throughput exceeds four billion liters/year. If emissions are priced, optimum design diameters typically increase to reduce pumping energy demands, increasing the cost-effectiveness of pipeline projects. Copyright © 2013 Elsevier Ltd. All rights reserved.

  17. Banning banking in EU emissions trading?

    International Nuclear Information System (INIS)

    Schleich, Joachim; Ehrhart, Karl-Martin; Hoppe, Christian; Seifert, Stefan

    2006-01-01

    Admitting banking in emissions trading systems reduces overall compliance costs by allowing for inter-temporal flexibility: cost savings can be traded over time. However, unless individual EU Member States (MS) decide differently, the transfer of unused allowances from the period of 2005-2007 into the first commitment period under the Kyoto Protocol, i.e. 2008-2012, will be prohibited. In this paper, we first explore the implications of such a ban on banking when initial emission targets are lenient. This analysis is based on a simulation which was recently carried out in Germany with companies and with a student control group. The findings suggest that a EU-wide ban on banking would lead to efficiency losses in addition to those losses which arise from the lack of inter-temporal flexibility. Second, we use simple game-theoretic considerations to argue that, under reasonable assumptions, such a EU-wide ban on banking will be the equilibrium outcome. Thus, to avoid a possible prisoners' dilemma, MS should have co-ordinated their banking decisions

  18. Analytical Method Details (MS): SE52_MS01 [Metabolonote[Archive

    Lifescience Database Archive (English)

    Full Text Available stem and Waters Q-Tof Premier UPLC-QTOF-MS ESI Negative The eluates (3 μl) were subsequently subjected to metabolome...DS column (LC-ESI-Q-Tof/MS, HPLC: Waters Acquity UPLC system; MS: Waters Q-Tof Premier). The metabolome...d (Matsuda et al., 2009c, 2010a). Briefly, the metabolome data were obtained in the negative ion mode (m/z 1... the complex nature of the metabolome data. To construct MS2T libraries, the extracts of five ecotypes were

  19. Information-dependent acquisition-mediated LC-MS/MS screening procedure with semiquantitative potential.

    Science.gov (United States)

    Decaestecker, Tineke N; Vande Casteele, Sofie R; Wallemacq, Pierre E; Van Peteghem, Carlos H; Defore, Dieter L; Van Bocxlaer, Jan F

    2004-11-01

    The development of a LC-MS/MS general unknown screening procedure for toxicologically relevant substances in blood samples by means of information-dependent acquisition on a Q-TOF is reported. IDA is an artificial intelligence-based product ion scan mode providing automatic "on-the-fly" MS to MS/MS switching. By performing information-dependent scanning at two different fragmentation energies, two collision-induced dissociation product ion spectra for each of the detected compounds are generated. As such, information-rich MS/MS spectra are obtained from precursor ions not known beforehand. In addition, limitation of the MS/MS acquisition time to an acceptable minimum resulted in an almost instantaneous switch back to the MS mode. As such, this approach provided MS chromatograms that still could be of use for semiquantitative purposes. Since the switching intensity threshold, unequivocally related to the background noise, proved a critical parameter, the solid-phase extraction procedure, the liquid chromatographic conditions, and the mass spectrometric parameters all were optimized to the advantage of information-dependent acquisition. Finally, the screening procedure we developed was benchmarked, on one hand, qualitatively against the results obtained from traditional GUS approaches in a number of routine toxicological laboratories (20 samples) and, on the other hand, quantitatively with respect to its potential against established LC-MS/MS methods (7 samples). The procedure performed very well from a qualitative point of view; almost all of the drugs detected by the conventional techniques were identified, as well as additional drugs that were not previously reported. The procedure proved well-suited for an initial semiquantitative assessment, as is customary in, for example, forensic toxicology before accurate intoxication levels are determined using targeted analytical analyses.

  20. On the application of ICP-MS techniques for measuring uranium and plutonium: a Nordic inter-laboratory comparison exercise

    DEFF Research Database (Denmark)

    Qiao, Jixin; Lagerkvist, Petra; Rodushkin, Ilia

    2018-01-01

    Inductively coupled plasma mass spectrometry (ICP-MS) techniques are widely used for determination of long-lived radionuclides and their isotopic ratios in the nuclear fields. Uranium (U) and Pu (Pu) isotopes have been determined by many researchers with ICP-MS due to its relatively high sensitiv...

  1. Delineation of cortical pathology in multiple sclerosis using multi-surface magnetization transfer ratio imaging

    Directory of Open Access Journals (Sweden)

    David A. Rudko

    2016-01-01

    Full Text Available The purpose of our study was to evaluate the utility of measurements of cortical surface magnetization transfer ratio (csMTR on the inner, mid and outer cortical boundaries as clinically accessible biomarkers of cortical gray matter pathology in multiple sclerosis (MS. Twenty-five MS patients and 12 matched controls were recruited from the MS Clinic of the Montreal Neurological Institute. Anatomical and magnetization transfer ratio (MTR images were acquired using 3 Tesla MRI at baseline and two-year time-points. MTR maps were smoothed along meshes representing the inner, mid and outer neocortical boundaries. To evaluate csMTR reductions suggestive of sub-pial demyelination in MS patients, a mixed model analysis was carried out at both the individual vertex level and in anatomically parcellated brain regions. Our results demonstrate that focal areas of csMTR reduction are most prevalent along the outer cortical surface in the superior temporal and posterior cingulate cortices, as well as in the cuneus and precentral gyrus. Additionally, age regression analysis identified that reductions of csMTR in MS patients increase with age but appear to hit a plateau in the outer caudal anterior cingulate, as well as in the precentral and postcentral cortex. After correction for the naturally occurring gradient in cortical MTR, the difference in csMTR between the inner and outer cortex in focal areas in the brains of MS patients correlated with clinical disability. Overall, our findings support multi-surface analysis of csMTR as a sensitive marker of cortical sub-pial abnormality indicative of demyelination in MS patients.

  2. Study of nuclear heat application systems for arresting CO2 emission

    International Nuclear Information System (INIS)

    Fumizawa, Motoo; Inaba, Yoshitomo; Hishida, Makoto; Ogata, Kan; Yamada, Seiya.

    1996-11-01

    The objective of the paper is to investigate the systems for arresting CO 2 emission and for the effective utilization of fossil fuel. We studied the fossil fuel reforming systems to decrease the CO 2 emission rate per unit amount of heat generation by fossil fuel. Feed materials for reforming system were natural gas, crude oil, oil sand, oil shale and coal. Products by reforming were hydrogen, methane, methanol and gasoline. We examined CO 2 emission ratio of ten systems with different feed material and product. The CO 2 emission ratio was the ratio of CO 2 emission rate per unit amount of heat generation between the products and the feed materials, and was the important index. As the results, the CO 2 emission ratio for the coal to methane reforming system using steam gasifier had the lowest value of 51%. It means that the CO 2 emission rate of the product from the coal to methane reforming system was 51% of the emission rate of the feed material, that is, the system is very effective to arrest the CO 2 emission. The CO 2 emission ratio increases in the following order: the reforming systems from coal to methanol, heavy oil to hydrogen and natural gas to hydrogen. It was clarified that the system of coal to methane reforming was very effective for arresting CO 2 emission compared to the other systems, moreover the nuclear heat using rate and thermal efficiency of the plant of the system were the highest. (author)

  3. Measurements of total lead concentrations and of lead isotope ratios in whole blood by use of inductively coupled plasma source mass spectrometry

    International Nuclear Information System (INIS)

    Delves, H.T.; Campbell, M.J.

    1988-01-01

    Methods are described for the accurate and precise determination of total lead and its isotopic composition in whole blood using inductively coupled plasma source mass spectrometry (ICP-MS). Sensitivities of up to 3 x 10 6 counts s -1 for 208 Pb at a total lead concentration of 5 μmol l -1 (1 μg ml -1 ) enabled total blood lead levels to be measured in 4 min per sample, with a detection limit of 0.072 μmol l -1 (15 μg l -1 ). The agreement between ICP-MS and atomic absorption spectrometry (AAS) for this analysis was excellent: ICP-MS 0.996 x AAS -0.0165 μmol l -1 ; r 0.994. Isotope ratio measurements required 15 min to achieve the required accuracy and precision both of which were generally better than 0.5% for 206 Pb: 207 Pb and 208 Pb: 206 Pb isotopic lead ratios. The ICP-MS data for these ratios in ten quality control blood specimens has a mean bias relative to isotope dilution mass spectrometry of -0.412% for 206 Pb: 207 Pb ratios and of +0.055% for the 208 Pb: 206 Pb ratios. This level of accuracy and that of the total blood lead measurements is sufficient to permit application of these ICP-MS methods to environmental studies. (author)

  4. Automated protein identification by the combination of MALDI MS and MS/MS spectra from different instruments.

    Science.gov (United States)

    Levander, Fredrik; James, Peter

    2005-01-01

    The identification of proteins separated on two-dimensional gels is most commonly performed by trypsin digestion and subsequent matrix-assisted laser desorption ionization (MALDI) with time-of-flight (TOF). Recently, atmospheric pressure (AP) MALDI coupled to an ion trap (IT) has emerged as a convenient method to obtain tandem mass spectra (MS/MS) from samples on MALDI target plates. In the present work, we investigated the feasibility of using the two methodologies in line as a standard method for protein identification. In this setup, the high mass accuracy MALDI-TOF spectra are used to calibrate the peptide precursor masses in the lower mass accuracy AP-MALDI-IT MS/MS spectra. Several software tools were developed to automate the analysis process. Two sets of MALDI samples, consisting of 142 and 421 gel spots, respectively, were analyzed in a highly automated manner. In the first set, the protein identification rate increased from 61% for MALDI-TOF only to 85% for MALDI-TOF combined with AP-MALDI-IT. In the second data set the increase in protein identification rate was from 44% to 58%. AP-MALDI-IT MS/MS spectra were in general less effective than the MALDI-TOF spectra for protein identification, but the combination of the two methods clearly enhanced the confidence in protein identification.

  5. Comparison of elemental quantity by PIXE and ICP-MS and/or ICP-AES for NIST standards

    International Nuclear Information System (INIS)

    Saitoh, K.; Sera, K.; Gotoh, T.; Nakamura, M.

    2002-01-01

    Urban particulate matter (SRM 1648), Buffalo River sediment (SRM 2704) and pine needle (SRM 1575) standard reference materials prepared by the National Institute of Standards and Technology (NIST, USA) were analyzed by three multi-element analysis methods, i.e., particle induced X-ray emission (PIXE), inductively coupled plasma-mass spectrometry (ICP-MS) and inductively coupled plasma-atomic emission spectrometry (ICP-AES); values determined by those analysis methods were compared with certified and/or non-certified values of NIST samples. Values determined by PIXE were 70-120% relative to certified and/or non-certified values of NIST samples except for Co in the urban particulate matter, for V and Co in Buffalo River sediment and for Ni and Br in the pine needles samples. In particular, Al, K, Ca, Cr, Mn, Fe, Cu, Zn and Pb were 85-110% in all samples. On the other hand, Na and Fe values determined by ICP-MS were very much different from the certified values in all samples, but the other elements were 70-120%. As for ICP-AES, all elements except for Na were 80-100% in all samples. Comparing the values determined by PIXE and those determined by ICP-MS and/or ICP-AES, there was a slight difference between the samples, but the range was 75-120% except for Na, V, Fe and Co determined by ICP-MS and Na determined by ICP-AES, which was generally consistent with PIXE

  6. Toward an Empirical Theory of Pulsar Emission. XII. Exploring the Physical Conditions in Millisecond Pulsar Emission Regions

    International Nuclear Information System (INIS)

    Rankin, Joanna M.; Mitra, Dipanjan; Archibald, Anne; Hessels, Jason; Leeuwen, Joeri van; Ransom, Scott; Stairs, Ingrid; Straten, Willem van; Weisberg, Joel M.

    2017-01-01

    The five-component profile of the 2.7 ms pulsar J0337+1715 appears to exhibit the best example to date of a core/double-cone emission-beam structure in a millisecond pulsar (MSP). Moreover, three other MSPs, the binary pulsars B1913+16, B1953+29, and J1022+1001, seem to exhibit core/single-cone profiles. These configurations are remarkable and important because it has not been clear whether MSPs and slow pulsars exhibit similar emission-beam configurations, given that they have considerably smaller magnetospheric sizes and magnetic field strengths. MSPs thus provide an extreme context for studying pulsar radio emission. Particle currents along the magnetic polar flux tube connect processes just above the polar cap through the radio-emission region to the light-cylinder and the external environment. In slow pulsars, radio-emission heights are typically about 500 km around where the magnetic field is nearly dipolar, and estimates of the physical conditions there point to radiation below the plasma frequency and emission from charged solitons by the curvature process. We are able to estimate emission heights for the four MSPs and carry out a similar estimation of physical conditions in their much lower emission regions. We find strong evidence that MSPs also radiate by curvature emission from charged solitons.

  7. Toward an Empirical Theory of Pulsar Emission. XII. Exploring the Physical Conditions in Millisecond Pulsar Emission Regions

    Energy Technology Data Exchange (ETDEWEB)

    Rankin, Joanna M.; Mitra, Dipanjan [Physics Department, University of Vermont, Burlington, VT 05405 (United States); Archibald, Anne; Hessels, Jason; Leeuwen, Joeri van [Anton Pannekoek Institute for Astronomy, University of Amsterdam, Science Park 904, 1098 XH Amsterdam (Netherlands); Ransom, Scott [National Radio Astronomy Observatory, Charlottesville, VA 29201 (United States); Stairs, Ingrid [Physics Department, University of British Columbia, V6T 1Z4, BC (Canada); Straten, Willem van [Institute for Radio Astronomy and Space Research, Auckland University of Technology, Auckland 1142 (New Zealand); Weisberg, Joel M., E-mail: Joanna.Rankin@uvm.edu [Physics and Astronomy Department, Carleton College, Northfield, MN 55057 (United States)

    2017-08-10

    The five-component profile of the 2.7 ms pulsar J0337+1715 appears to exhibit the best example to date of a core/double-cone emission-beam structure in a millisecond pulsar (MSP). Moreover, three other MSPs, the binary pulsars B1913+16, B1953+29, and J1022+1001, seem to exhibit core/single-cone profiles. These configurations are remarkable and important because it has not been clear whether MSPs and slow pulsars exhibit similar emission-beam configurations, given that they have considerably smaller magnetospheric sizes and magnetic field strengths. MSPs thus provide an extreme context for studying pulsar radio emission. Particle currents along the magnetic polar flux tube connect processes just above the polar cap through the radio-emission region to the light-cylinder and the external environment. In slow pulsars, radio-emission heights are typically about 500 km around where the magnetic field is nearly dipolar, and estimates of the physical conditions there point to radiation below the plasma frequency and emission from charged solitons by the curvature process. We are able to estimate emission heights for the four MSPs and carry out a similar estimation of physical conditions in their much lower emission regions. We find strong evidence that MSPs also radiate by curvature emission from charged solitons.

  8. Emissions characteristics of higher alcohol/gasoline blends

    International Nuclear Information System (INIS)

    Gautam, M.; Martin, D.W.; Carder, D.

    2000-01-01

    An experimental investigation was conducted to determine the emissions characteristics of higher alcohols and gasoline (UTG96) blends. While lower alcohols (methanol and ethanol) have been used in blends with gasoline, very little work has been done or reported on higher alcohols (propanol, butanol and pentanol). Comparisons of emissions and fuel characteristics between higher alcohol/gasoline blends and neat gasoline were made to determine the advantages and disadvantages of blending higher alcohols with gasoline. All tests were conducted on a single-cylinder Waukesha Cooperative Fuel Research engine operating at steady state conditions and stoichiometric air-fuel (A/F) ratio. Emissions test were conducted at the optimum spark timing-knock limiting compression ratio combination for the particular blend being tested. The cycle emission [mass per unit time (g/h)] of CO, CO 2 and organic matter hydrocarbon equivalent (OMHCE) from the higher alcohol/gasoline blends were very similar to those from neat gasoline. Cycle emissions of NO x from the blends were higher than those from neat gasoline. However, for all the emissions species considered, the brake specific emissions (g/kW h) were significantly lower for the higher alcohol/gasoline blends than for neat gasoline. This was because the blends had greater resistance to knock and allowed higher compression ratios, which increased engine power output. The contribution of alcohols and aldehydes to the overall OMHCE emissions was found to be minimal. Cycle fuel consumption (g/h) of higher alcohol/gasoline blends was slightly higher than with neat gasoline due to the lower stoichiometric A/F ratios required by the blends. However, the brake specific fuel consumption (g/kW h) for the blends was significantly lower than that for neat gasoline. (Author)

  9. Millimeter-wave Line Ratios and Sub-beam Volume Density Distributions

    Energy Technology Data Exchange (ETDEWEB)

    Leroy, Adam K.; Gallagher, Molly [Department of Astronomy, The Ohio State University, 140 West 18th Avenue, Columbus, OH 43210 (United States); Usero, Antonio [Observatorio Astronmico Nacional (IGN), C/Alfonso XII, 3, E-28014 Madrid (Spain); Schruba, Andreas [Max-Planck-Institut für extraterrestrische Physik, Giessenbachstraße 1, D-85748 Garching (Germany); Bigiel, Frank [Institute für theoretische Astrophysik, Zentrum für Astronomie der Universität Heidelberg, Albert-Ueberle Str. 2, D-69120 Heidelberg (Germany); Kruijssen, J. M. Diederik; Schinnerer, Eva [Astronomisches Rechen-Institut, Zentrum für Astronomie der Universität Heidelberg, Mönchhofstraße 12-14, D-69120 Heidelberg (Germany); Kepley, Amanda [National Radio Astronomy Observatory, 520 Edgemont Road, Charlottesville, VA 22903 (United States); Blanc, Guillermo A. [Departamento de Astronomía, Universidad de Chile, Casilla 36-D, Santiago (Chile); Bolatto, Alberto D. [Department of Astronomy, Laboratory for Millimeter-wave Astronomy, and Joint Space Institute, University of Maryland, College Park, MD 20742 (United States); Cormier, Diane; Jiménez-Donaire, Maria J. [Max Planck Institute für Astronomie, Königstuhl 17, D-69117, Heidelberg (Germany); Hughes, Annie [CNRS, IRAP, 9 av. du Colonel Roche, BP 44346, F-31028 Toulouse cedex 4 (France); Rosolowsky, Erik [Department of Physics, University of Alberta, Edmonton, AB (Canada)

    2017-02-01

    We explore the use of mm-wave emission line ratios to trace molecular gas density when observations integrate over a wide range of volume densities within a single telescope beam. For observations targeting external galaxies, this case is unavoidable. Using a framework similar to that of Krumholz and Thompson, we model emission for a set of common extragalactic lines from lognormal and power law density distributions. We consider the median density of gas that produces emission and the ability to predict density variations from observed line ratios. We emphasize line ratio variations because these do not require us to know the absolute abundance of our tracers. Patterns of line ratio variations have the potential to illuminate the high-end shape of the density distribution, and to capture changes in the dense gas fraction and median volume density. Our results with and without a high-density power law tail differ appreciably; we highlight better knowledge of the probability density function (PDF) shape as an important area. We also show the implications of sub-beam density distributions for isotopologue studies targeting dense gas tracers. Differential excitation often implies a significant correction to the naive case. We provide tabulated versions of many of our results, which can be used to interpret changes in mm-wave line ratios in terms of adjustments to the underlying density distributions.

  10. Dental diagnostic clinical instrument ('Canary') development using photothermal radiometry and modulated luminescence

    Energy Technology Data Exchange (ETDEWEB)

    Jeon, R J; Sivagurunathan, K; Garcia, J; Matvienko, A; Mandelis, A [Center for Advanced Diffusion Wave Technologies (CADIFT), Department of Mechanical and Industrial Engineering, University of Toronto, 5 King' s College Road, Toronto, Ontario, M5S 3G8 (Canada); Abrams, S, E-mail: mandelis@mie.utoronto.c [Quantum Dental Technologies, 748 Briar Hill Avenue, Toronto, Ontario, M6B 1L3 (Canada)

    2010-03-01

    Since 1999, our group at the CADIFT, University of Toronto, has developed the application of Frequency Domain Photothermal Radiometry (PTR) and Luminescence (LUM) to dental caries detection. Various cases including artificial caries detection have been studied and some of the inherent advantages of the adaptation of this technique to dental diagnostics in conjunction with modulated luminescence as a dual-probe technique have been reported. Based on these studies, a portable, compact diagnostic instrument for dental clinic use has been designed, assembled and tested. A semiconductor laser, optical fibers, a thermoelectric cooled mid-IR detector, and a USB connected data acquisition card were used. Software lock-in amplifier techniques were developed to compute amplitude and phase of PTR and LUM signals. In order to achieve fast measurement and acceptable signal-to-noise ratio (SNR) for clinical application, swept sine waveforms were used. As a result sampling and stabilization time for each measurement point was reduced to a few seconds. A sophisticated software interface was designed to simultaneously record intra-oral camera images with PTR and LUM responses. Preliminary results using this instrument during clinical trials in a dental clinic showed this instrument could detect early caries both from PTR and LUM signals.

  11. Dental diagnostic clinical instrument (Canary) development using photothermal radiometry and modulated luminescence

    International Nuclear Information System (INIS)

    Jeon, R J; Sivagurunathan, K; Garcia, J; Matvienko, A; Mandelis, A; Abrams, S

    2010-01-01

    Since 1999, our group at the CADIFT, University of Toronto, has developed the application of Frequency Domain Photothermal Radiometry (PTR) and Luminescence (LUM) to dental caries detection. Various cases including artificial caries detection have been studied and some of the inherent advantages of the adaptation of this technique to dental diagnostics in conjunction with modulated luminescence as a dual-probe technique have been reported. Based on these studies, a portable, compact diagnostic instrument for dental clinic use has been designed, assembled and tested. A semiconductor laser, optical fibers, a thermoelectric cooled mid-IR detector, and a USB connected data acquisition card were used. Software lock-in amplifier techniques were developed to compute amplitude and phase of PTR and LUM signals. In order to achieve fast measurement and acceptable signal-to-noise ratio (SNR) for clinical application, swept sine waveforms were used. As a result sampling and stabilization time for each measurement point was reduced to a few seconds. A sophisticated software interface was designed to simultaneously record intra-oral camera images with PTR and LUM responses. Preliminary results using this instrument during clinical trials in a dental clinic showed this instrument could detect early caries both from PTR and LUM signals.

  12. The Venus flytrap attracts insects by the release of volatile organic compounds.

    Science.gov (United States)

    Kreuzwieser, Jürgen; Scheerer, Ursel; Kruse, Jörg; Burzlaff, Tim; Honsel, Anne; Alfarraj, Saleh; Georgiev, Plamen; Schnitzler, Jörg-Peter; Ghirardo, Andrea; Kreuzer, Ines; Hedrich, Rainer; Rennenberg, Heinz

    2014-02-01

    Does Dionaea muscipula, the Venus flytrap, use a particular mechanism to attract animal prey? This question was raised by Charles Darwin 140 years ago, but it remains unanswered. This study tested the hypothesis that Dionaea releases volatile organic compounds (VOCs) to allure prey insects. For this purpose, olfactory choice bioassays were performed to elucidate if Dionaea attracts Drosophila melanogaster. The VOCs emitted by the plant were further analysed by GC-MS and proton transfer reaction-mass spectrometry (PTR-MS). The bioassays documented that Drosophila was strongly attracted by the carnivorous plant. Over 60 VOCs, including terpenes, benzenoids, and aliphatics, were emitted by Dionaea, predominantly in the light. This work further tested whether attraction of animal prey is affected by the nutritional status of the plant. For this purpose, Dionaea plants were fed with insect biomass to improve plant N status. However, although such feeding altered the VOC emission pattern by reducing terpene release, the attraction of Drosophila was not affected. From these results it is concluded that Dionaea attracts insects on the basis of food smell mimicry because the scent released has strong similarity to the bouquet of fruits and plant flowers. Such a volatile blend is emitted to attract insects searching for food to visit the deadly capture organ of the Venus flytrap.

  13. Elemental composition of current automotive braking materials and derived air emission factors

    Science.gov (United States)

    Hulskotte, J. H. J.; Roskam, G. D.; Denier van der Gon, H. A. C.

    2014-12-01

    Wear-related PM emissions are an important constituent of total PM emissions from road transport. Due to ongoing (further) exhaust emission reduction wear emissions may become the dominant PM source from road transport in the near future. The chemical composition of the wear emissions is crucial information to assess the potential health relevance of these PM emissions. Here we provide an elemental composition profile of brake wear emissions as used in the Netherlands in 2012. In total, 65 spent brake pads and 15 brake discs were collected in car maintenance shops from in-use personal cars vehicles and analyzed with XRF for their metal composition (Fe, Cu, Zn, Sn, Al, Si, Zr, Ti, Sb, Cr, Mo, Mn, V, Ni, Bi, W, P, Pb and Co). Since car, engine and safety regulations are not nationally determined but controlled by European legislation the resulting profiles will be representative for the European personal car fleet. The brake pads contained Fe and Cu as the dominant metals but their ratio varied considerably, other relatively important metals were Sn, Zn and Sb. Overall a rather robust picture emerged with Fe, Cu, Zn and Sn together making up about 80-90% of the metals present in brake pads. Because the XRF did not give information on the contents of other material such as carbon, oxygen and sulphur, a representative selection of 9 brake pads was further analyzed by ICP-MS and a carbon and sulphur analyzer. The brake pads contained about 50% of non-metal material (26% C, 3% S and the remainder mostly oxygen and some magnesium). Based on our measurements, the average brake pad profile contained 20% Fe, 10% Cu, 4% Zn and 3% Sn as the dominant metals. The brake discs consisted almost entirely of metal with iron being the dominant metal (>95%) and only traces of other metals (<1% for individual metals). Non-metal components in the discs were 2-3% Silicon and, according to literature, ∼3% carbon. The robust ratio between Fe and Cu as found on kerbsides has been used to

  14. Molecular analysis of intact preen waxes of Calidris Canutus (Aves: Scolopacidae) by GC/MS and GC/MS/MS

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Dekker, M.H.A.; Piersma, T.

    2000-01-01

    The intact preen wax esters of the red knot Calidris canutus were studied with gas chromatography/mass spectrometry (GC/MS) and GC/MS/MS. In this latter technique, transitions from the molecular ion to fragment ions representing the fatty acid moiety of the wax esters were measured, providing

  15. Analysis of plutonium isotopes in marine samples by radiometric, ICP-MS and AMS techniques

    International Nuclear Information System (INIS)

    Lee, S.H.; Gastaud, J.; La Rosa, J.J.; Liong Wee Kwong, L.; Povinec, P.P.; Wyse, E.

    2001-01-01

    IAEA reference materials (radionuclides in the marine environment) collected in areas affected by nuclear reprocessing plants and nuclear weapons tests have been analysed by semiconductor alpha-spectrometry (SAS), liquid scintillation spectrometry (LSS) and mass spectrometric techniques (high resolution ICP-MS and AMS) with the aim of developing analytical procedures and to study the geochemical behavior of plutonium in the marine environment. The Pu results obtained by SAS, ICP-MS and AMS were in reasonably good agreement (R 2 = 0.99). The mean atom ratios of 240 Pu/ 239 Pu in IAEA reference materials, IAEA-134, 135 and 381 were (0.212±0.010), (0.211±0.004) and (0.242±0.004), respectively. IAEA-384 (Fangataufa Lagoon Sediment) gave a 240 Pu/ 239 Pu mean atom ratio of 0.051±0.001. The results of 241 Pu obtained buy ICP-MS and LSS also show reasonable agreement (R 2 = 0.91). Pu isotopic signatures were useful in tracing Pu origin and in interpreting biogeochemical processes involving Pu in the marine environment. (author)

  16. A NEW CLASS OF NASCENT ECLIPSING BINARIES WITH EXTREME MASS RATIOS

    Energy Technology Data Exchange (ETDEWEB)

    Moe, Maxwell; Stefano, Rosanne Di, E-mail: mmoe@cfa.harvard.edu [Harvard-Smithsonian Center for Astrophysics, 60 Garden Street, MS-10, Cambridge, MA 02138 (United States)

    2015-03-10

    Early B-type main-sequence (MS) stars (M {sub 1} ≈ 5-16 M {sub ☉}) with closely orbiting low-mass stellar companions (q = M {sub 2}/M {sub 1} < 0.25) can evolve to produce Type Ia supernovae, low-mass X-ray binaries, and millisecond pulsars. However, the formation mechanism and intrinsic frequency of such close extreme mass-ratio binaries have been debated, especially considering none have hitherto been detected. Utilizing observations of the Large Magellanic Cloud galaxy conducted by the Optical Gravitational Lensing Experiment, we have discovered a new class of eclipsing binaries in which a luminous B-type MS star irradiates a closely orbiting low-mass pre-MS companion that has not yet fully formed. The primordial pre-MS companions have large radii and discernibly reflect much of the light they intercept from the B-type MS primaries (ΔI {sub refl} ≈ 0.02-0.14 mag). For the 18 definitive MS + pre-MS eclipsing binaries in our sample with good model fits to the observed light-curves, we measure short orbital periods P = 3.0-8.5 days, young ages τ ≈ 0.6-8 Myr, and small secondary masses M {sub 2} ≈ 0.8-2.4 M {sub ☉} (q ≈ 0.07-0.36). The majority of these nascent eclipsing binaries are still associated with stellar nurseries, e.g., the system with the deepest eclipse ΔI {sub 1} = 2.8 mag and youngest age τ = 0.6 ± 0.4 Myr is embedded in the bright H II region 30 Doradus. After correcting for selection effects, we find that (2.0 ± 0.6)% of B-type MS stars have companions with short orbital periods P = 3.0-8.5 days and extreme mass ratios q ≈ 0.06-0.25. This is ≈10 times greater than that observed for solar-type MS primaries. We discuss how these new eclipsing binaries provide invaluable insights, diagnostics, and challenges for the formation and evolution of stars, binaries, and H II regions.

  17. [Triglycerides/HDL-cholesterol ratio: in adolescents without cardiovascular risk factors].

    Science.gov (United States)

    Soutelo, Jimena; Graffigna, Mabel; Honfi, Margarita; Migliano, Marta; Aranguren, Marcela; Proietti, Adrian; Musso, Carla; Berg, Gabriela

    2012-06-01

    Triglycerides/HDL-cholesterol ratio (TG/HDL) is an easy resource determination and it has good correlation with the HOMA index in adults. Due to physiological insulin resistance (IR) in adolescence it is necessary to find markers of IR independent of age, sex and pubertal stage. The objective was to identify reference values of TG/HDL ratio in a population of adolescents without cardiovascular risk factors. We evaluated 943 adolescents, 429 females and 514 males between 11 and 14. Anthropometric measures were determined and body mass index was calculated (BMI). Blood was extracted after 12 hours of fasting to determine glucose, triglycerides, HDL. The metabolic syndrome (MS) was diagnosed according to criteria of NCEP/ATP III modified by Cook. We excluded adolescents with MS or any component of it. We evaluated 562 adolescents (289 women and 273 men) with a weight of 48.91 +/- 6.51kg, BMI: 18.95 +/- 1.78, systolic blood pressure of 108.12 +/- 13.60 mmHg, diastolic blood pressure: 63.82 +/- 9.43 and waist circumference: 65.09 +/- 4.54 cm. TG/HDL ratio was 1.25 +/- 0.43, with a 95 percentile of 2.05. In adults, TG/HDL ratio greater than 3 is a marker of insulin resistance. We believe that a higher value to 2.05 might be a good index of insulin resistance in adolescence. TG/HDL ratio has the advantage of being methodologically simpler, more economical and independent of pubertal stage.

  18. Intron-Mediated Alternative Splicing of WOOD-ASSOCIATED NAC TRANSCRIPTION FACTOR1B Regulates Cell Wall Thickening during Fiber Development in Populus Species1[W

    Science.gov (United States)

    Zhao, Yunjun; Sun, Jiayan; Xu, Peng; Zhang, Rui; Li, Laigeng

    2014-01-01

    Alternative splicing is an important mechanism involved in regulating the development of multicellular organisms. Although many genes in plants undergo alternative splicing, little is understood of its significance in regulating plant growth and development. In this study, alternative splicing of black cottonwood (Populus trichocarpa) wood-associated NAC domain transcription factor (PtrWNDs), PtrWND1B, is shown to occur exclusively in secondary xylem fiber cells. PtrWND1B is expressed with a normal short-transcript PtrWND1B-s as well as its alternative long-transcript PtrWND1B-l. The intron 2 structure of the PtrWND1B gene was identified as a critical sequence that causes PtrWND1B alternative splicing. Suppression of PtrWND1B expression specifically inhibited fiber cell wall thickening. The two PtrWND1B isoforms play antagonistic roles in regulating cell wall thickening during fiber cell differentiation in Populus spp. PtrWND1B-s overexpression enhanced fiber cell wall thickening, while overexpression of PtrWND1B-l repressed fiber cell wall thickening. Alternative splicing may enable more specific regulation of processes such as fiber cell wall thickening during wood formation. PMID:24394777

  19. Intron-mediated alternative splicing of WOOD-ASSOCIATED NAC TRANSCRIPTION FACTOR1B regulates cell wall thickening during fiber development in Populus species.

    Science.gov (United States)

    Zhao, Yunjun; Sun, Jiayan; Xu, Peng; Zhang, Rui; Li, Laigeng

    2014-02-01

    Alternative splicing is an important mechanism involved in regulating the development of multicellular organisms. Although many genes in plants undergo alternative splicing, little is understood of its significance in regulating plant growth and development. In this study, alternative splicing of black cottonwood (Populus trichocarpa) wood-associated NAC domain transcription factor (PtrWNDs), PtrWND1B, is shown to occur exclusively in secondary xylem fiber cells. PtrWND1B is expressed with a normal short-transcript PtrWND1B-s as well as its alternative long-transcript PtrWND1B-l. The intron 2 structure of the PtrWND1B gene was identified as a critical sequence that causes PtrWND1B alternative splicing. Suppression of PtrWND1B expression specifically inhibited fiber cell wall thickening. The two PtrWND1B isoforms play antagonistic roles in regulating cell wall thickening during fiber cell differentiation in Populus spp. PtrWND1B-s overexpression enhanced fiber cell wall thickening, while overexpression of PtrWND1B-l repressed fiber cell wall thickening. Alternative splicing may enable more specific regulation of processes such as fiber cell wall thickening during wood formation.

  20. Relapsing-Remitting MS (RRMS)

    Medline Plus

    Full Text Available ... Definition of MS Myelin Immune-Mediated Disease T Cells d What Causes MS? Disproved Theories Viruses Clusters ... d Research News & Progress Research News MSPARIS2017 Stem Cells in MS Progressive MS Research Clinical Trials in ...

  1. Body mass index during adolescence, rather than childhood, is critical in determining MS risk.

    Science.gov (United States)

    Hedström, A K; Olsson, T; Alfredsson, L

    2016-06-01

    Obesity in childhood and during adolescence has repeatedly been associated with increased risk of developing multiple sclerosis (MS). We aimed to investigate whether the most critical period occurs during childhood or later, during adolescence. Using a population-based case-control study (1586 cases and 2800 controls), individuals with different body sizes at age 10 and different body mass indices at age 20 were compared regarding MS risk, by calculating odds ratios with 95% confidence intervals. Potential interactions between HLA-DRB1*15 and absence of HLA-A*02, respectively, and both childhood and adolescent obesity were evaluated by calculating the attributable proportion due to interaction. Regardless of body size at age 10, individuals with adolescent obesity had a 90% increased risk of MS. Among participants who were not obese at age 20, no association was observed between body size at age 10 and subsequent MS risk. An interaction was observed between the HLA MS risk genes and adolescent, but not childhood, obesity. Our results suggest that BMI during adolescence, rather than childhood, is critical in determining MS risk. © The Author(s), 2015.

  2. Development of an SPME-GC-MS method for the specific quantification of dimethylamine and trimethylamine: use of a new ratio for the freshness monitoring of cod fillets.

    Science.gov (United States)

    Dehaut, Alexandre; Duthen, Simon; Grard, Thierry; Krzewinski, Frédéric; N'Guessan, Assi; Brisabois, Anne; Duflos, Guillaume

    2016-08-01

    Fish is a highly perishable food, so it is important to be able to estimate its freshness to ensure optimum quality for consumers. The present study describes the development of an SPME-GC-MS technique capable of quantifying both trimethylamine (TMA) and dimethylamine (DMA), components of what has been defined as partial volatile basic nitrogen (PVB-N). This method was used, together with other reference methods, to monitor the storage of cod fillets (Gadus morhua) conserved under melting ice. Careful optimisation enabled definition of the best parameters for extracting and separating targeted amines and an internal standard. The study of cod spoilage by sensory analysis and TVB-N assay led to the conclusion that the shelf-life of cod fillet was between 6 and 7 days. Throughout the study, TMA and DMA were specifically quantified by SPME-GC-MS; the first was found to be highly correlated with the values returned by steam distillation assays. Neither TMA-N nor DMA-N were able to successfully characterise the decrease in early freshness, unlike dimethylamine/trimethylamine ratio (DTR), whose evolution is closely related to the results of sensory analysis until the stage where fillets need to be rejected. DTR was proposed as a reliable indicator for the early decrease of freshness until fish rejection. © 2015 Society of Chemical Industry. © 2015 Society of Chemical Industry.

  3. Relapsing-Remitting MS (RRMS)

    Medline Plus

    Full Text Available ... MS Relapsing-remitting MS (RRMS) Share this page Facebook Twitter Email Relapsing-remitting MS (RRMS) Relapsing-remitting ... Here Start Here Colophon Stay Informed Join Us Facebook Twitter LinkedIn YouTube Pinterest MS Connection About the ...

  4. Relapsing-Remitting MS (RRMS)

    Medline Plus

    Full Text Available ... d Living Well with MS d Diet, Exercise & Healthy Behaviors Diet & Nutrition Exercise Heat & Temperature Sensitivity Sleep Vaccinations Women's Health Unhealthy Habits Managing MS and Another Condition Aging with MS Anesthesia and Surgery Managing Your MS ...

  5. Relapsing-Remitting MS (RRMS)

    Medline Plus

    Full Text Available ... to navigation Skip to content Menu Navigation National Multiple Sclerosis Society Sign In In Your Area Donate Donate ... of MS What Causes MS? Who Gets MS? Multiple Sclerosis FAQs Types of MS Related Conditions Symptoms & Diagnosis ...

  6. Relapsing-Remitting MS (RRMS)

    Medline Plus

    Full Text Available ... Relapsing-remitting MS (RRMS) Share this page Facebook Twitter Email Relapsing-remitting MS (RRMS) Relapsing-remitting MS ( ... Start Here Colophon Stay Informed Join Us Facebook Twitter LinkedIn YouTube Pinterest MS Connection About the Society ...

  7. 54. Annual symposium of the Austrian Physical Society; 54. Jahrestagung der Oesterreichischen Physikalischen Gesellschaft

    Energy Technology Data Exchange (ETDEWEB)

    Lippitsch, M [Institut fuer Experimentalphysik, Universitaet Graz, Universitaetsplatz 5, Graz (Austria)

    2004-07-01

    The papers presented were organized under the following sessions: main session (from attoseconds to RGB to telecom, density functional calculations, magnetic anisotropy of nanostructures, quantum cascade laser, bose-einstein condensates, DNA molecular force sensor); Fritz-Kohlrausch-price 2004 (nanoscale building blocks), Max-Auwaerter-price 2004 (electron emission and nano defects, magnetic rings), AT + S price 2004 (conducting atomic-force microscopy for nanoscale studies), Viktor-Hess-price 2004 (entanglement for meson-antimeson systems), Roman-Ulrich-Sexl-price 2004 (teaching physics ); acoustics; atomic-, molecular- and plasma physics (kinetic electron emission, accelerated-mass spectrometry of molecules, dissociative electron attachment, voc measurements); solid physics (spin relaxation, nano clean room reactor, proton transport through nanotubes); nuclear and particle physics (color reconnection, supersymmetry at Large Hadron Collider, pionic hydrogen, kaonic hydrogen, quantum chaos, quantum dwell time, trigger system simulation, ATLAS initial detector layout, QCD); medical-, bio-and environmental physics (PTR-MS, validation Monte Carlo FLUKA codes, Gamma camera- positron emission tomography); neutrons and synchrotron radiation physics (3D synchrotron micro on human bones); surface and thin film analysis; quantum electronics, electrodynamics and optics (teleportation, optic induced changes in interaction in BEC, electronic feed back cooling single ions) and poster sessions with topics dealing with the subjects above mentioned. This book of abstracts contains their summaries and those contributions which are in the INIS subject scope are indexed individually. (nevyjel)

  8. 54. Annual symposium of the Austrian Physical Society

    International Nuclear Information System (INIS)

    Lippitsch, M.

    2004-01-01

    The papers presented were organized under the following sessions: main session (from attoseconds to RGB to telecom, density functional calculations, magnetic anisotropy of nanostructures, quantum cascade laser, bose-einstein condensates, DNA molecular force sensor); Fritz-Kohlrausch-price 2004 (nanoscale building blocks), Max-Auwaerter-price 2004 (electron emission and nano defects, magnetic rings), AT + S price 2004 (conducting atomic-force microscopy for nanoscale studies), Viktor-Hess-price 2004 (entanglement for meson-antimeson systems), Roman-Ulrich-Sexl-price 2004 (teaching physics ); acoustics; atomic-, molecular- and plasma physics (kinetic electron emission, accelerated-mass spectrometry of molecules, dissociative electron attachment, voc measurements); solid physics (spin relaxation, nano clean room reactor, proton transport through nanotubes); nuclear and particle physics (color reconnection, supersymmetry at Large Hadron Collider, pionic hydrogen, kaonic hydrogen, quantum chaos, quantum dwell time, trigger system simulation, ATLAS initial detector layout, QCD); medical-, bio-and environmental physics (PTR-MS, validation Monte Carlo FLUKA codes, Gamma camera- positron emission tomography); neutrons and synchrotron radiation physics (3D synchrotron micro on human bones); surface and thin film analysis; quantum electronics, electrodynamics and optics (teleportation, optic induced changes in interaction in BEC, electronic feed back cooling single ions) and poster sessions with topics dealing with the subjects above mentioned. This book of abstracts contains their summaries and those contributions which are in the INIS subject scope are indexed individually. (nevyjel)

  9. Sesquiterpene volatile organic compounds (VOCs are markers of elicitation by sulfated laminarine in grapevine

    Directory of Open Access Journals (Sweden)

    Malik eChalal

    2015-05-01

    Full Text Available Inducing resistance in plants by application of elicitors of defense reactions is an attractive plant protection strategy, especially for grapevine (Vitis vinifera which is susceptible to severe fungal diseases. Though induced resistance (IR can be successful in controlled conditions, under outdoor conditions IR is in most cases not effective enough for practical disease control. Progress in the application of IR requires a better understanding of grapevine defense mechanisms and the ability to monitor defense markers in order to identify factors (physiological, environmental… that can impact IR in the vineyard.Volatile organic compounds (VOCs are well-known plant defenses compounds that have only received little or no attention in the case of grape-pathogen interactions to date. This prompted us to investigate whether an elicitor, the sulfated laminarin (PS3, actually induces the production of VOCs in grapevine. Online analysis (PTR-QMS of VOC emissions in dynamic cuvettes and passive sampling in gas tight bags with solid phase micro extraction (SPME-GC-MS under greenhouse conditions showed that PS3 elicited emission of VOCs. Some of them (as (E,E-α-farnesene might be good candidates as biomarkers of elicitor-IR whereas methyl salicylate appears to be rather a biomarker of downy mildew infection. A negative correlation between VOC emission and disease severity suggests a positive role of VOCs in grape defense against diseases.

  10. A Ratio-Analysis Method to the Dynamics of Excited State Proton Transfer: Pyranine in Water and Micelles.

    Science.gov (United States)

    Sahu, Kalyanasis; Nandi, Nilanjana; Dolai, Suman; Bera, Avisek

    2018-06-05

    Emission spectrum of a fluorophore undergoing excited state proton transfer (ESPT) often exhibits two distinct bands each representing emissions from protonated and deprotonated forms. The relative contribution of the two bands, best represented by an emission intensity ratio (R) (intensity maximum of the protonated band / intensity maximum of the deprotonated band), is an important parameter which usually denotes feasibility or promptness of the ESPT process. However, the use of ratio is only limited to the interpretation of steady-state fluorescence spectra. Here, for the first time, we exploit the time-dependence of the ratio (R(t)), calculated from time-resolved emission spectra (TRES) at different times, to analyze ESPT dynamics. TRES at different times were fitted with a sum of two lognormal-functions representing each peaks and then, the peak intensity ratio, R(t) was calculated and further fitted with an analytical function. Recently, a time-resolved area-normalized emission spectra (TRANES)-based analysis was presented where the decay of protonated emission or the rise of deprotonated emission intensity conveniently accounts for the ESPT dynamics. We show that these two methods are equivalent but the new method provides more insights on the nature of the ESPT process.

  11. Intensive measurements of gas, water, and energy exchange between vegetation and troposphere during the MONTES campaign in a vegetation gradient from short semi-desertic shrublands to tall wet temperate forests in the NW Mediterranean Basin

    Science.gov (United States)

    Peñuelas, J.; Guenther, A.; Rapparini, F.; Llusia, J.; Filella, I.; Seco, R.; Estiarte, M.; Mejia-Chang, M.; Ogaya, R.; Ibañez, J.; Sardans, J.; Castaño, L. M.; Turnipseed, A.; Duhl, T.; Harley, P.; Vila, J.; Estavillo, J. M.; Menéndez, S.; Facini, O.; Baraldi, R.; Geron, C.; Mak, J.; Patton, E. G.; Jiang, X.; Greenberg, J.

    2013-08-01

    MONTES (“Woodlands”) was a multidisciplinary international field campaign aimed at measuring energy, water and especially gas exchange between vegetation and atmosphere in a gradient from short semi-desertic shrublands to tall wet temperate forests in NE Spain in the North Western Mediterranean Basin (WMB). The measurements were performed at a semidesertic area (Monegros), at a coastal Mediterranean shrubland area (Garraf), at a typical Mediterranean holm oak forest area (Prades) and at a wet temperate beech forest (Montseny) during spring (April 2010) under optimal plant physiological conditions in driest-warmest sites and during summer (July 2010) with drought and heat stresses in the driest-warmest sites and optimal conditions in the wettest-coolest site. The objective of this campaign was to study the differences in gas, water and energy exchange occurring at different vegetation coverages and biomasses. Particular attention was devoted to quantitatively understand the exchange of biogenic volatile organic compounds (BVOCs) because of their biological and environmental effects in the WMB. A wide range of instruments (GC-MS, PTR-MS, meteorological sensors, O3 monitors,…) and vertical platforms such as masts, tethered balloons and aircraft were used to characterize the gas, water and energy exchange at increasing footprint areas by measuring vertical profiles. In this paper we provide an overview of the MONTES campaign: the objectives, the characterization of the biomass and gas, water and energy exchange in the 4 sites-areas using satellite data, the estimation of isoprene and monoterpene emissions using MEGAN model, the measurements performed and the first results. The isoprene and monoterpene emission rates estimated with MEGAN and emission factors measured at the foliar level for the dominant species ranged from about 0 to 0.2 mg m-2 h-1 in April. The warmer temperature in July resulted in higher model estimates from about 0 to ca. 1.6 mg m-2 h-1 for

  12. Detection and differentiation of 22kDa and 20kDa Growth Hormone proteoforms in human plasma by LC-MS/MS

    DEFF Research Database (Denmark)

    Sanmartín, Gerard Such; Bache, N.; Bosch, J.

    2015-01-01

    Human growth hormone (GH) is suspected to be widely and illegally used in sport to improve athletes' performance. For the detection of GH abuse, blood samples are screened for abnormal ratios between the 22 and 20kDa GH proteoforms that demonstrate the administration of the synthetic hormone....... Current detection methods are based on classical immunoassays as they provide sufficient sensitivity for the detection of GH proteoforms. These antibody based methods, however, suffer from unclear selectivity and potential cross-reactivity towards similar proteins. For unambiguous GH detection, we report...... a Mass Spectrometry ImmunoAssay (MSIA) that first enriches GH from plasma with an antibody of relatively low specificity, and subsequently quantifies the 22 and 20kDa proteoforms by Selected Reaction Monitoring (SRM) LC-MS/MS analysis. This method proved superior to an antibody-free strategy based on GH...

  13. Ecosystem scale VOC exchange measurements at Bosco Fontana (IT) and Hyytiälä (FI)

    Science.gov (United States)

    Schallhart, S.; Rantala, P.; Taipale, R.; Nemitz, E.; Tillmann, R.; Mentel, T. F.; Ruuskanen, T.; Rinne, J.

    2013-12-01

    monoterpenes storages, which are emitted at high temperatures. The results of both forests are consistent with the cuvette measurements of Ghirardo et al. (2010). This research received funding from the EC Seventh Framework Programme (Collaborative project "ECLAIRE" grant no. 282910) and by the Academy of Finland Center of Excellence program (project number 141135). References.: Ghirardo, A., Koch, K., Taipale, R., Zimmer, I., Schnitzler, J-P. and Rinne, J. Determination of de novo and pool emissions of terpenes from four common boreal/alpine trees by 13CO2 labelling and PTR-MS analysis. Plant, Cell & Environment,33,5,781-792,2010. Taipale, R., Kajos, M.K., Patokoski, J., Rantala, P., Ruuskanen, T.M. and Rinne, J. Role of de novo biosynthesis in ecosystem scale monoterpene emissions from a boreal Scots pine forest. Biogeosciences, 8, 8, 2247-2255, 2011.

  14. Relapsing-Remitting MS (RRMS)

    Medline Plus

    Full Text Available ... the Challenges of MS You CAN! Webcasts DVDs Books For Kids: Keep S'myelin Información en Español Brochures ... Managing MS and Another Condition Aging with MS Anesthesia and Surgery Managing Your MS d Emotional Well- ...

  15. Relapsing-Remitting MS (RRMS)

    Medline Plus

    Full Text Available ... the Challenges of MS You CAN! Webcasts DVDs Books For Kids: Keep S'myelin Información en Español Brochures ... MS Managing MS Resources for You and Your Practice Publications for Clinicians Publications for Your Patients MS ...

  16. Noise Emission of a 200 kW Vertical Axis Wind Turbine

    Directory of Open Access Journals (Sweden)

    Erik Möllerström

    2015-12-01

    Full Text Available The noise emission from a vertical axis wind turbine (VAWT has been investigated. A noise measurement campaign on a 200 kW straight-bladed VAWT has been conducted, and the result has been compared to a semi-empirical model for turbulent-boundary-layer trailing edge (TBL-TE noise. The noise emission from the wind turbine was measured, at wind speed 8 m/s, 10 m above ground, to 96.2 dBA. At this wind speed, the turbine was stalling as it was run at a tip speed lower than optimal due to constructional constraints. The noise emission at a wind speed of 6 m/s, 10 m above ground was measured while operating at optimum tip speed and was found to be 94.1 dBA. A comparison with similar size horizontal axis wind turbines (HAWTs indicates a noise emission at the absolute bottom of the range. Furthermore, it is clear from the analysis that the turbulent-boundary-layer trailing-edge noise, as modeled here, is much lower than the measured levels, which suggests that other mechanisms are likely to be important, such as inflow turbulence.

  17. Intercomparison of Volatile Organic Carbon Measurement Techniques and Data at La Porte During the TexAQS2000 Air Quality Study

    Energy Technology Data Exchange (ETDEWEB)

    Kuster, W. C.; Jobson, B Tom T.; Karl, Thomas G.; Riemer, D.; Apel, Eric; Goldan, P. D.; Fehsenfeld, Fred C.

    2004-01-01

    The Texas Air Quality Study 2000 (TexAQS2000) investigated the photochemical production of ozone and the chemistry of related precursors and reaction products in the vicinity of Houston, Texas. The co-location of four instruments for the measurement of volatile organic carbon compounds (VOCs) allowed a unique opportunity for the intercomparison of the different in-situ measuring techniques. The instruments included three gas chromatographs, each with a different type of detector, and a Proton-Transfer-Reaction Mass Spectrometer (PTR-MS) with each system designed to measure a different suite of VOCs. Correlation plots and correlation statistics are presented for species measured by more than one of these instruments. The GC instruments were all in agreement to within 10-20% (slope) with coefficients of variation (r2) of {ge} 0.85. The PTR-MS agreement with other instruments was more dependent on species with some very good agreements (r2 values of {approx}0.95 for some aromatics) but isoprene, acetaldehyde and propene were substantially less highly correlated (0.55 < r2 < 0.80). At least part of these differences were undoubtedly due to the timing of sample acquisition in an environment in which VOC levels changed very rapidly on both quantitative and temporal scales.

  18. Monitoring benzene formation from benzoate in model systems by proton transfer reaction-mass spectrometry

    Science.gov (United States)

    Aprea, Eugenio; Biasioli, Franco; Carlin, Silvia; Märk, Tilmann D.; Gasperi, Flavia

    2008-08-01

    The presence of benzene in food and in particular in soft drinks has been reported in several studies and should be considered in fundamental investigations about formation of this carcinogen compound as well as in quality control. Proton transfer reaction-mass spectrometry (PTR-MS) has been used here for rapid, direct quantification of benzene and to monitor its formation in model systems related to the use of benzoate, a common preservative, in presence of ascorbic acid: a widespread situation that yields benzene in, e.g., soft drinks and fruit juices. Firstly, we demonstrate here that PTR-MS allows a rapid determination of benzene that is in quantitative agreement with independent solid phase micro-extraction/gas chromatography (SPME/GC) analysis. Secondly, as a case study, the effect of different sugars (sucrose, fructose and glucose) on benzene formation is investigated indicating that they inhibit its formation and that this effect is enhanced for reducing sugars. The sugar-induced inhibition of benzene formation depends on several parameters (type and concentration of sugar, temperature, time) but can be more than 80% in situations that can be expected in the storage of commercial soft drinks. This is consistent with the reported observations of higher benzene concentrations in sugar-free soft drinks.

  19. Chemometrically assisted development and validation of LC-MS/MS method for the analysis of potential genotoxic impurities in meropenem active pharmaceutical ingredient.

    Science.gov (United States)

    Grigori, Katerina; Loukas, Yannis L; Malenović, Anđelija; Samara, Vicky; Kalaskani, Anastasia; Dimovasili, Efi; Kalovidouri, Magda; Dotsikas, Yannis

    2017-10-25

    A sensitive Liquid Chromatography tandem mass spectrometry (LC-MS/MS) method was developed and validated for the quantitative analysis of three potential genotoxic impurities (318BP, M9, S5) in meropenem Active Pharmaceutical Ingredient (API). Due to the requirement for LOD values in ppb range, a high concentration of meropenem API (30mg/mL) had to be injected. Therefore, efficient determination of meropenem from its impurities became a critical aim of this study, in order to divert meropenem to waste, via a switching valve. ‎ After the selection of the important factors affecting analytes' elution, a Box-Behnken design was utilized to set the plan of experiments conducted with UV detector. As responses, the separation factor s between the last eluting impurity and meropenem, as well as meropenem retention factor k were used. Grid point search methodology was implemented aiming to obtain the optimal conditions that simultaneously comply to the conflicted criteria. Optimal mobile phase consisted of ACN, methanol and 0.09% HCOOH at a ratio 71/3.5/15.5v/v. All impurities and internal standard omeprazole were eluted before 7.5min and at 8.0min the eluents were directed to waste. The protocol was transferred to LC-MS/MS and validated according to ICH guidelines. Copyright © 2017 Elsevier B.V. All rights reserved.

  20. Mass spectrometric measurement of urinary kynurenine-to-tryptophan ratio in children with and without urinary tract infection.

    Science.gov (United States)

    Yarbrough, Melanie L; Briden, Kelleigh E; Mitsios, John V; Weindel, Annette L; Terrill, Cindy M; Hunstad, David A; Dietzen, Dennis J

    2018-04-19

    Indoleamine-2,3-dioxygenase (IDO) catalyzes the first step of tryptophan (Trp) catabolism, yielding kynurenine (Kyn) metabolites. The kynurenine-to-tryptophan (K/T) ratio is used as a surrogate for biological IDO enzyme activity. IDO expression is increased during Escherichia coli urinary tract infection (UTI). Thus, our objective was to develop a method for measurement of Kyn/Trp ratio in human blood and urine and evaluate its use as a biomarker of UTI. A mass spectrometric method was developed to measure Trp and Kyn in serum and urine specimens. The method was applied to clinical urine specimens from symptomatic pediatric patients with laboratory-confirmed UTI or other acute conditions and from healthy controls. The liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was linear to 500 μmol/L for both Trp and Kyn. Imprecision ranged from 5 to 15% for Trp and 6-20% for Kyn. Analytical recoveries of Trp and Kyn ranged from 96 to 119% in serum and 90-97% in urine. No correlation was found between the K/T ratio and circulating IDO mass (r = 0.110) in serum. Urinary Kyn and Trp in the pediatric test cohort demonstrated elevations in the K/T ratio in symptomatic patients with UTI (median 13.08) and without UTI (median 14.38) compared to healthy controls (median 4.93; p < 0.001 for both comparisons). No significant difference in K/T ratio was noted between symptomatic patients with and without UTI (p = 0.84). Measurement of Trp and Kyn by LC-MS/MS is accurate and precise in serum and urine specimens. While urinary K/T ratio is not a specific biomarker for UTI, it may represent a general indicator of a systemic inflammatory process. Copyright © 2018 The Canadian Society of Clinical Chemists. Published by Elsevier Inc. All rights reserved.

  1. pDeep: Predicting MS/MS Spectra of Peptides with Deep Learning.

    Science.gov (United States)

    Zhou, Xie-Xuan; Zeng, Wen-Feng; Chi, Hao; Luo, Chunjie; Liu, Chao; Zhan, Jianfeng; He, Si-Min; Zhang, Zhifei

    2017-12-05

    In tandem mass spectrometry (MS/MS)-based proteomics, search engines rely on comparison between an experimental MS/MS spectrum and the theoretical spectra of the candidate peptides. Hence, accurate prediction of the theoretical spectra of peptides appears to be particularly important. Here, we present pDeep, a deep neural network-based model for the spectrum prediction of peptides. Using the bidirectional long short-term memory (BiLSTM), pDeep can predict higher-energy collisional dissociation, electron-transfer dissociation, and electron-transfer and higher-energy collision dissociation MS/MS spectra of peptides with >0.9 median Pearson correlation coefficients. Further, we showed that intermediate layer of the neural network could reveal physicochemical properties of amino acids, for example the similarities of fragmentation behaviors between amino acids. We also showed the potential of pDeep to distinguish extremely similar peptides (peptides that contain isobaric amino acids, for example, GG = N, AG = Q, or even I = L), which were very difficult to distinguish using traditional search engines.

  2. Recent Developments in Trace, Ultratrace and Isotope Ratio Measurements in Inductively Coupled Plasma Mass Spectrometry

    International Nuclear Information System (INIS)

    Zahran, N. F.

    2004-01-01

    Inductively coupled plasma mass spectrometry (ICP-MS) and Laser Ablation (LA-ICP-MS) are recent techniques for trace, ultratrace and isotope ratio measurements. Main features of these techniques and their figure of merit and capabilities are discussed. An overview of ICP-MS instrument is presented in addition to its precision, accuracy and detection limits. Uses of ICP-MS in environmental monitoring in some cases for detection of some radio nuclides are presented. Two geological applications namely, zircon grains analysis and age dating of Rb-Sr method are presented. Zn elemental and isotopic analyses in blood and serum as a biological application is shown. (Author)

  3. Unambiguous Metabolite Identification in High-Throughput Metabolomics by Hybrid 1H-NMR/ESI-MS1 Approach

    Energy Technology Data Exchange (ETDEWEB)

    2016-10-18

    The invention improves accuracy of metabolite identification by combining direct infusion ESI-MS with one-dimensional 1H-NMR spectroscopy. First, we apply a standard 1H-NMR metabolite identification protocol by matching the chemical shift, J-coupling and intensity information of experimental NMR signals against the NMR signals of standard metabolites in a metabolomics reference libraries. This generates a list of candidate metabolites. The list contains both false positive and ambiguous identifications. The software tool (the invention) takes the list of candidate metabolites, generated from NMRbased metabolite identification, and then calculates, for each of the candidate metabolites, the monoisotopic mass-tocharge (m/z) ratios for each commonly observed ion, fragment and adduct feature. These are then used to assign m/z ratios in experimental ESI-MS spectra of the same sample. Detection of the signals of a given metabolite in both NMR and MS spectra resolves the ambiguities, and therefore, significantly improves the confidence of the identification.

  4. Similarity ratio analysis for early stage fault detection with optical emission spectrometer in plasma etching process.

    Directory of Open Access Journals (Sweden)

    Jie Yang

    Full Text Available A Similarity Ratio Analysis (SRA method is proposed for early-stage Fault Detection (FD in plasma etching processes using real-time Optical Emission Spectrometer (OES data as input. The SRA method can help to realise a highly precise control system by detecting abnormal etch-rate faults in real-time during an etching process. The method processes spectrum scans at successive time points and uses a windowing mechanism over the time series to alleviate problems with timing uncertainties due to process shift from one process run to another. A SRA library is first built to capture features of a healthy etching process. By comparing with the SRA library, a Similarity Ratio (SR statistic is then calculated for each spectrum scan as the monitored process progresses. A fault detection mechanism, named 3-Warning-1-Alarm (3W1A, takes the SR values as inputs and triggers a system alarm when certain conditions are satisfied. This design reduces the chance of false alarm, and provides a reliable fault reporting service. The SRA method is demonstrated on a real semiconductor manufacturing dataset. The effectiveness of SRA-based fault detection is evaluated using a time-series SR test and also using a post-process SR test. The time-series SR provides an early-stage fault detection service, so less energy and materials will be wasted by faulty processing. The post-process SR provides a fault detection service with higher reliability than the time-series SR, but with fault testing conducted only after each process run completes.

  5. Ferro-based derivatizing agents for LC/MS an LC/EC/MS

    NARCIS (Netherlands)

    Seiwert, Bettina

    2007-01-01

    Within this thesis, the development and application of ferrocene-based derivatizing agents for LC/MS and LC/EC/MS is presented. The advantages of derivatization by ferrocenes are the similtaneous introduction of a mass tag and an electroactive group, which make them ideally suited for LC/MS and

  6. Isotopic Ratios of Samarium by TIMS for Nuclear Forensic Application

    Energy Technology Data Exchange (ETDEWEB)

    Louis Jean, James [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Inglis, Jeremy David [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2017-08-08

    The isotopic ratio of Nd, Sm, and Gd can provide important information regarding fissile material (nuclear devices, reactors), neutron environment, and device yield. These studies require precise measurement of Sm isotope ratios, by either TIMS or MC-ICP-MS. There has been an increasing trend to measure smaller and smaller quantities of Sm bearing samples. In nuclear forensics 10-100 ng of Sm are needed for precise measurement. To measure sub-ng Sm samples using TIMS for nuclear forensic analysis.

  7. Application of CE-ICP-MS and CE-ESI-MS/MS for identification of Zn-binding ligands in Goji berries extracts.

    Science.gov (United States)

    Ruzik, Lena; Kwiatkowski, Piotr

    2018-06-01

    The identification of groups of ligands binding metals is a crucial issue for the better understanding of their bioaccessibility. In the current study, we have intended an approach for identification of Zn-binding ligands based on using capillary electrophoresis combined with inductively coupled plasma mass spectrometry (CE-ICP-MS) and tandem electrospray ionization mass spectrometry (CE-ESI-MS/MS). The approach, which featured the use of the coupling of capillary electrophoresis with inductively coupled plasma mass spectrometry allows to separate and observe zinc ions present in complexes with respect to their size and charge and to identify nine compounds with zinc isotopic profile. CE-ICP-MS provides us with information about presence of zinc species and elemental information about zinc distribution. CE-ESI-MS/MS provide us with information about the most favorable Zn binding ligands: amino acids, flavonols, stilbenoids, fenolic acids and carotenoids. The presented work is the continuation of previous studies based on using LC-ESI-MS/MS, though, now we presented a new solutions with the possibility of changing detectors without changing the separation techniques, what is important without re-optimizing the method. The new presented method allows to identify the zinc-binding ligands in shorter time. Copyright © 2018 Elsevier B.V. All rights reserved.

  8. Total OH reactivity study from VOC photochemical oxidation in the SAPHIR chamber

    Science.gov (United States)

    Yu, Z.; Tillmann, R.; Hohaus, T.; Fuchs, H.; Novelli, A.; Wegener, R.; Kaminski, M.; Schmitt, S. H.; Wahner, A.; Kiendler-Scharr, A.

    2015-12-01

    It is well known that hydroxyl radicals (OH) act as a dominant reactive species in the degradation of VOCs in the atmosphere. In recent field studies, directly measured total OH reactivity often showed poor agreement with OH reactivity calculated from VOC measurements (e.g. Nölscher et al., 2013; Lu et al., 2012a). This "missing OH reactivity" is attributed to unaccounted biogenic VOC emissions and/or oxidation products. The comparison of total OH reactivity being directly measured and calculated from single component measurements of VOCs and their oxidation products gives us a further understanding on the source of unmeasured reactive species in the atmosphere. This allows also the determination of the magnitude of the contribution of primary VOC emissions and their oxidation products to the missing OH reactivity. A series of experiments was carried out in the atmosphere simulation chamber SAPHIR in Jülich, Germany, to explore in detail the photochemical degradation of VOCs (isoprene, ß-pinene, limonene, and D6-benzene) by OH. The total OH reactivity was determined from the measurement of VOCs and their oxidation products by a Proton Transfer Reaction Time of Flight Mass Spectrometer (PTR-TOF-MS) with a GC/MS/FID system, and directly measured by a laser-induced fluorescence (LIF) at the same time. The comparison between these two total OH reactivity measurements showed an increase of missing OH reactivity in the presence of oxidation products of VOCs, indicating a strong contribution to missing OH reactivity from uncharacterized oxidation products.

  9. Analysis of pesticide residues in strawberries and soils by GC-MS/MS, LC-MS/MS and two-dimensional GC-time-of-flight MS comparing organic and integrated pest management farming.

    Science.gov (United States)

    Fernandes, Virgínia C; Lehotay, Steven J; Geis-Asteggiante, Lucía; Kwon, Hyeyoung; Mol, Hans G J; van der Kamp, Henk; Mateus, Nuno; Domingues, Valentina F; Delerue-Matos, Cristina

    2014-01-01

    This study analysed 22 strawberry and soil samples after their collection over the course of 2 years to compare the residue profiles from organic farming with integrated pest management practices in Portugal. For sample preparation, we used the citrate-buffered version of the quick, easy, cheap, effective, rugged, and safe (QuEChERS) method. We applied three different methods for analysis: (1) 27 pesticides were targeted using LC-MS/MS; (2) 143 were targeted using low pressure GC-tandem mass spectrometry (LP-GC-MS/MS); and (3) more than 600 pesticides were screened in a targeted and untargeted approach using comprehensive, two-dimensional gas chromatography time-of-flight mass spectrometry (GC × GC-TOF-MS). Comparison was made of the analyses using the different methods for the shared samples. The results were similar, thereby providing satisfactory confirmation of both similarly positive and negative findings. No pesticides were found in the organic-farmed samples. In samples from integrated pest management practices, nine pesticides were determined and confirmed to be present, ranging from 2 µg kg(-1) for fluazifop-p-butyl to 50 µg kg(-1) for fenpropathrin. Concentrations of residues in strawberries were less than European maximum residue limits.

  10. Quantitative Determination of Perfluorochemicals and Fluorotelomer Alcohols in Plants from Biosolid-Amended Fields using LC/MS/MS and GC/MS

    Science.gov (United States)

    Analytical methods for determining perfluorochemicals (PFCs) and fluorotelomer alcohols (FTOHs) in plants using liquid chromatography/tandem mass spectrometry (LC/MS/MS) and gas chromatography/mass spectrometry (GC/MS) were developed, and applied to quantify a suite of analytes i...

  11. In Vivo Metabolism Study of Xiamenmycin A in Mouse Plasma by UPLC-QTOF-MS and LC-MS/MS

    Directory of Open Access Journals (Sweden)

    Feng Lei

    2015-01-01

    Full Text Available Xiamenmycin A is an antifibrotic leading compound with a benzopyran skeleton that is isolated from mangrove-derived Streptomyces xiamenensis. As a promising small molecule for fibrotic diseases, less information is known about its metabolic characteristics in vivo. In this study, the time-course of xiamenmycin A in mouse plasma was investigated by relative quantification. After two types of administration of xiamenmycin A at a single dose of 10 mg/kg, the plasma concentrations were measured quantitatively by LC-MS/MS. The dynamic changes in the xiamenmycin A concentration showed rapid absorption and quick elimination in plasma post-administration. Four metabolites (M1–M4 were identified in blood by UPLC-QTOF-MS, and xiamenmycin B (M3 is the principal metabolite in vivo, as verified by comparison of the authentic standard sample. The structures of other metabolites were identified based on the characteristics of their MS and MS/MS data. The newly identified metabolites are useful for understanding the metabolism of xiamenmycin A in vivo, aiming at the development of an anti-fibrotic drug candidate for the therapeutic treatment of excessive fibrotic diseases.

  12. Relapsing-Remitting MS (RRMS)

    Medline Plus

    Full Text Available ... Become an MS Activist Take Action Current Advocacy Issues Advocacy Results Advocacy News d Raise Awareness d ... MS are more likely to experience gradually worsening problems with walking and mobility, along with whatever other symptoms they may have. Diagnosing relapsing-remitting MS (RRMS) Learn More Learn More ... Room MS Prevalence ...

  13. Measurements of oxygenated volatile organic compounds in the oil sands region of Alberta

    Science.gov (United States)

    Moussa, S. G.; Leithead, A.; Li, S. M.; Gordon, M.; Hayden, K. L.; Wang, D. K.; Staebler, R. M.; Liu, P.; O'Brien, J.; Mittermeier, R.; Liggio, J.

    2014-12-01

    Oxygenated volatile organic compounds (OVOCs) are ubiquitous in the atmosphere, and represent an important fraction of volatile organic compounds. Additionally some OVOC species may pose health risks. OVOCs can affect the oxidative and radiative budget of the atmosphere since they are precursors to ground level ozone, hydroxyl radicals and secondary organic aerosols (SOA). OVOCs such as methanol, formaldehyde, acetaldehyde, acetone, crotonaldehyde, methylvinylketone (MVK), methylethylketone (MEK) and acrolein can be emitted from anthropogenic and biogenic sources. Additionally, they are the secondary products of the photo-oxidation of hydrocarbons (biogenic and anthropogenic). Understanding the magnitude of these sources is a prerequisite for accurate representations of radical cycling, ozone production and SOA formation in air quality models. The sources of OVOCs in the Alberta Oil Sands (OS) region have not previously been well characterized. In the summer of 2013, airborne measurements of various OVOCs were made in the Athabasca oil sands region between August 13 and September 7, 2013. Proton Transfer Reaction-Time of Flight-Mass Spectrometry (PTR-ToF-MS) was used to measure methanol, formaldehyde, acetaldehyde, acetone, crotonaldehyde, MVK, MEK, acrolein as well as other hydrocarbons. Emission ratios (ER) for several OVOCs (relative to carbon monoxide; CO) were used to estimate direct anthropogenic emissions from OS industrial sources, while the calculated OH radical exposures were used to estimate the production and removal of secondary anthropogenic OVOCs. The results indicate that OVOCs such as acetaldehyde, crotonaldehyde and MVK have both primary and secondary anthropogenic and biogenic sources. However, species such as methanol and acrolein are from biogenic and anthropogenic sources, respectively. The results of this work will help to characterize sources of OVOCs and the factors influencing their atmospheric fate in the Oil Sands region.

  14. Experimental evaluation of the effect of compression ratio on performance and emission of SI engine fuelled with gasoline and n-butanol blend at different loads

    Directory of Open Access Journals (Sweden)

    Rinu Thomas

    2016-09-01

    Full Text Available Never ending demand for efficient and less polluting engines have always inspired newer technologies. Extensive study has been done on variable compression ratio, a promising in-cylinder technology, in the recent past. The present work is an experimental investigation to examine the variation of different parameters such as brake thermal efficiency, exhaust gas temperature and emissions with respect to change in compression ratio in a single-cylinder carbureted SI engine at different loads with two different fuels. Experiments were conducted at three different compression ratios (CR = 7:1, 8.5:1 and 10:1. The fuels used in this study are pure gasoline and 20% n-butanol blend (B20 in gasoline. The results showed that brake thermal efficiency increases with CR at all loads. Further, the experimental results showed the scope of improving the part-load efficiency of SI engine by adopting the concept of variable compression ratio (VCR technology, especially when fuels with better anti-knock characteristics are used. The uncertainty analysis of the experiments based on the specifications of the equipment used is also tabulated.

  15. Survey of diagnostic and treatment practices for multiple sclerosis (MS) in Europe. Part 2: Progressive MS, paediatric MS, pregnancy and general management.

    Science.gov (United States)

    Fernández, O; Delvecchio, M; Edan, G; Fredrikson, S; Giovannoni, G; Hartung, H-P; Havrdova, E; Kappos, L; Pozzilli, C; Soerensen, P S; Tackenberg, B; Vermersch, P; Comi, G

    2018-05-01

    The European Charcot Foundation supported the development of a set of surveys to understand current practice patterns for the diagnosis and management of multiple sclerosis (MS) in Europe. Part 2 of the report summarizes survey results related to secondary progressive MS (SPMS), primary progressive MS (PPMS), pregnancy, paediatric MS and overall patient management. A steering committee of MS neurologists developed case- and practice-based questions for two sequential surveys distributed to MS neurologists throughout Europe. Respondents generally favoured changing rather than stopping disease-modifying treatment (DMT) in patients transitioning from relapsing-remitting MS to SPMS, particularly with active disease. Respondents would not initiate DMT in patients with typical PPMS symptoms, although the presence of ≥1 spinal cord or brain gadolinium-enhancing lesion might affect that decision. For patients considering pregnancy, respondents were equally divided on whether to stop treatment before or after conception. Respondents strongly favoured starting DMT in paediatric MS with active disease; recommended treatments included interferon, glatiramer acetate and, in John Cunningham virus negative patients, natalizumab. Additional results regarding practice-based questions and management are summarized. Results of part 2 of the survey of diagnostic and treatment practices for MS in Europe largely mirror results for part 1, with neurologists in general agreement about the treatment and management of SPMS, PPMS, pregnancy and paediatric MS as well as the general management of MS. However, there are also many areas of disagreement, indicating the need for evidence-based recommendations and/or guidelines. © 2018 EAN.

  16. Sulphur fertilization influences the sulphur species composition in Allium sativum: sulphomics using HPLC-ICPMS/MS-ESI-MS/MS.

    Science.gov (United States)

    Raab, Andrea; Ronzan, Marilena; Feldmann, Joerg

    2017-10-18

    Garlic (A. sativum) contains a large number of small sulphur (S)-containing metabolites, which are important for its taste and smell and vary with A. sativum variety and growth conditions. This study was designed to investigate the influence of different sulphur-fertilization regimes on low molecular weight S-species by attempting the first sulphur mass balance in A. sativum roots and bulbs using HPLC-ICPMS/MS-ESI-MS/MS. Species unspecific quantification of acid soluble S-containing metabolites was achieved using HPLC-ICP-MS/MS. For identification of the compounds, high resolution ESI-MS (Orbitrap LTQ and q-TOF) was used. The plants contained up to 54 separated sulphur-containing compounds, which constitute about 80% of the total sulphur present in A. sativum. The roots and bulbs of A. sativum contained the same compounds, but not necessarily the same amounts and proportions. The S-containing metabolites in the roots reacted more sensitively to manipulations of sulphur fertilization than those compounds in the bulbs. In addition to known compounds (e.g. γ-glutamyl-S-1-propenylcysteine) we were able to identify and partially quantify 31 compounds. Three as yet undescribed S-containing compounds were also identified and quantified for the first time. Putative structures were assigned to the oxidised forms of S-1-propenylmercaptoglutathione, S-2-propenylmercaptoglutathione, S-allyl/propenyl-containing PC-2 and 2-amino-3-[(2-carboxypropyl)sulfanyl]propanoic acid. The parallel use of ICP-MS/MS as a sulphur-specific detector and ESI-MS as a molecular detector simplifies the identification and quantification of sulphur containing metabolites without species specific standards. This non-target analysis approach enables a mass balance approach and identifies the occurrence of the so far unidentified organosulphur compounds. The experiments showed that the sulphur-fertilization regime does not influence sulphur-speciation, but the concentration of some S

  17. Performance of a carbon nanotube field emission electron gun

    Science.gov (United States)

    Getty, Stephanie A.; King, Todd T.; Bis, Rachael A.; Jones, Hollis H.; Herrero, Federico; Lynch, Bernard A.; Roman, Patrick; Mahaffy, Paul

    2007-04-01

    A cold cathode field emission electron gun (e-gun) based on a patterned carbon nanotube (CNT) film has been fabricated for use in a miniaturized reflectron time-of-flight mass spectrometer (RTOF MS), with future applications in other charged particle spectrometers, and performance of the CNT e-gun has been evaluated. A thermionic electron gun has also been fabricated and evaluated in parallel and its performance is used as a benchmark in the evaluation of our CNT e-gun. Implications for future improvements and integration into the RTOF MS are discussed.

  18. Reduction of Solvent Effect in Reverse Phase Gradient Elution LC-ICP-MS

    Energy Technology Data Exchange (ETDEWEB)

    Sullivan, Patrick Allen [Iowa State Univ., Ames, IA (United States)

    2005-12-17

    Quantification in liquid chromatography (LC) is becoming very important as more researchers are using LC, not as an analytical tool itself, but as a sample introduction system for other analytical instruments. The ability of LC instrumentation to quickly separate a wide variety of compounds makes it ideal for analysis of complex mixtures. For elemental speciation, LC is joined with inductively coupled plasma mass spectrometry (ICP-MS) to separate and detect metal-containing, organic compounds in complex mixtures, such as biological samples. Often, the solvent gradients required to perform complex separations will cause matrix effects within the plasma. This limits the sensitivity of the ICP-MS and the quantification methods available for use in such analyses. Traditionally, isotope dilution has been the method of choice for LC-ICP-MS quantification. The use of naturally abundant isotopes of a single element in quantification corrects for most of the effects that LC solvent gradients produce within the plasma. However, not all elements of interest in speciation studies have multiple naturally occurring isotopes; and polyatomic interferences for a given isotope can develop within the plasma, depending on the solvent matrix. This is the case for reverse phase LC separations, where increasing amounts of organic solvent are required. For such separations, an alternative to isotope dilution for quantification would be is needed. To this end, a new method was developed using the Apex-Q desolvation system (ESI, Omaha, NE) to couple LC instrumentation with an ICP-MS device. The desolvation power of the system allowed greater concentrations of methanol to be introduced to the plasma prior to destabilization than with direct methanol injection into the plasma. Studies were performed, using simulated and actual linear methanol gradients, to find analyte-internal standard (AIS) pairs whose ratio remains consistent (deviations {+-} 10%) over methanol concentration ranges of 5

  19. Studying the effect of compression ratio on an engine fueled with waste oil produced biodiesel/diesel fuel

    Directory of Open Access Journals (Sweden)

    Mohammed EL_Kassaby

    2013-03-01

    Full Text Available Wasted cooking oil from restaurants was used to produce neat (pure biodiesel through transesterification, and then used to prepare biodiesel/diesel blends. The effect of blending ratio and compression ratio on a diesel engine performance has been investigated. Emission and combustion characteristics was studded when the engine operated using the different blends (B10, B20, B30, and B50 and normal diesel fuel (B0 as well as when varying the compression ratio from 14 to 16 to 18. The result shows that the engine torque for all blends increases as the compression ratio increases. The bsfc for all blends decreases as the compression ratio increases and at all compression ratios bsfc remains higher for the higher blends as the biodiesel percent increase. The change of compression ratio from 14 to 18 resulted in, 18.39%, 27.48%, 18.5%, and 19.82% increase in brake thermal efficiency in case of B10, B20, B30, and B50 respectively. On an average, the CO2 emission increased by 14.28%, the HC emission reduced by 52%, CO emission reduced by 37.5% and NOx emission increased by 36.84% when compression ratio was increased from 14 to 18. In spite of the slightly higher viscosity and lower volatility of biodiesel, the ignition delay seems to be lower for biodiesel than for diesel. On average, the delay period decreased by 13.95% when compression ratio was increased from 14 to 18. From this study, increasing the compression ratio had more benefits with biodiesel than that with pure diesel.

  20. FeII/MgII Emission Line Ratio in High Redshift Quasars

    DEFF Research Database (Denmark)

    Dietrich, M.; Hamann, F.; Appenzeller, I.

    2003-01-01

    the evolution of the FeII/MgII ratio over a wider range in cosmic time, we measured this ratio for composite quasar spectra which cover a redshift range of 0 4 quasars must have started already at an epoch corresponding to z_f = 6 to 9, when the age of the universe was ~0.5 Gyr (H_o = 72 km/s/Mpc, Omega_M = 0...